TW201303507A - Pattern forming method, multilayer resist pattern, multilayer film for organic solvent development, method of manufacturing electronic component, and electronic component - Google Patents

Abstract

The present invention provides a pattern forming method comprising: (i) a step of forming a first film on a substrate by using the first resin composition (I); (ii) using a film different from the resin composition (I) a second resin composition (II) forming a second film on the first film; (iii) a step of exposing the multilayer film having the first film and the second film; and (iv) developing by using an organic solvent The step of developing the first film of the exposed multilayer film and the second film to form a negative pattern.

Description

Pattern forming method, multilayer resist pattern, multilayer film for organic solvent development, resist composition, method of manufacturing electronic component, and electronic component

The present invention relates to a pattern forming method suitable for manufacturing a semiconductor (such as an IC) or a process for manufacturing a liquid crystal element or a circuit board (such as a thermal head) and additionally suitable for lithography in other photoprocessing processes, a multilayer anti-layer An etchant pattern, a multilayer film for organic solvent development, a resist composition suitable for the pattern forming method, a method for producing an electronic device, and an electronic device. More specifically, the present invention relates to a pattern forming method, a multilayer resist pattern, a multilayer film for organic solvent development, a method for producing an electronic device, and an electronic device which are suitable for exposure by an ArF or KrF exposure apparatus.

Since the appearance of resists for KrF excimer lasers (248 nm), an imaging method called chemical amplification has been used as a resist imaging method to compensate for sensitivity due to light absorption. reduce. For example, an imaging method achieved by positive chemical amplification is an imaging method that decomposes an acid generator in an exposed region to generate an acid upon exposure to an excimer laser, an electron beam, an extreme ultraviolet light, or the like, Thus, in the post-exposure bake (PEB: Post Exposure Bake), the alkali-insoluble group is converted into an alkali-soluble group by using the generated acid as a reaction catalyst, and the exposed region is removed by an alkali developer.

For the alkali developer used in the above method, various alkali developers have been proposed, but an aqueous alkali developer containing 2.38 mass% TMAH (aqueous tetramethylammonium hydroxide solution) is generally used.

In addition, as the application of the above resist technology, micromachining applications, Ion implantation (charge injection, a step in the processing of logic elements or the like) used in the implantation of ions is under development.

In the case where the resist composition is used for ion implantation applications, the resist composition is sometimes coated, exposed, and developed on a previously patterned substrate (hereinafter referred to as a stepped substrate). And the stepped substrate needs to be micromachined. When applied to ion implantation, the difficult task involved in the patterning of micromachining for development with the above-mentioned alkali developer is the scum problem on the substrate, and the scum is due to the resist composition after development. The film formed is poor in release properties.

In order to meet the needs of such a micromachining technology, not only a positive resist which is currently dominant, but also a method of forming a fine pattern by a negative image is being developed (see, for example, JP-A-2010-40849). (The term "JP-A" as used herein means "unexamined published Japanese patent application"), JP-A-2008-292975 and JP-A-2010-217884). This is because, in the fabrication of a semiconductor element or the like, it is necessary to form a pattern having various contours such as lines, grooves, and cavities, and some patterns are difficult to form by the current positive type resist.

The present inventors have found that, for example, according to a negative pattern forming method developed by an organic solvent, the problem of scumming on a substrate due to development with the above-described alkali developer in patterning of microfabrication can be solved.

However, the negative pattern forming method by organic solvent development faces a problem that the pattern easily has an undercut profile. In addition, in roughness performance, such as line width roughness (line width roughness, There is still room for improvement in LWR).

In view of the above problems, it is an object of the present invention to provide a pattern forming method capable of forming a pattern having a good line width roughness (LWR) while having a rectangular outline, a multilayer resist pattern formed by the method, and being suitable for A multilayer film for organic solvent development of the pattern forming method, a resist composition suitable for the pattern forming method, a method for producing an electronic device, and an electronic component.

The present inventors have completed the present invention because of intensive studies to achieve the above object.

That is, the present invention has the following configuration.

[1] A pattern forming method comprising: (i) a step of forming a first film on a substrate by using the first resin composition (I); (ii) using a film different from the resin composition (I) a second resin composition (II) forming a second film on the first film; (iii) a step of exposing the multilayer film having the first film and the second film; and (iv) developing by using an organic solvent And a step of developing the first film and the second film of the exposed multilayer film to form a negative pattern.

[2] The pattern forming method according to [1], wherein the resin contained in the first resin composition (I) is different from the resin contained in the second resin composition (II).

[3] The pattern forming method according to [1] or [2], wherein at least one of the first resin composition (I) and the second resin composition (II) includes one A specific resin containing a repeating unit having a group capable of decomposing to generate a polar group by an acid.

[4] The pattern forming method according to any one of [1] to [3] wherein a solubility parameter SP1 and a second resin composition of the resin contained in the first resin composition (I) The solubility parameter SP2 of the resin contained in (II) has the relationship of the following formula (1), and the resin contained in the first resin composition (I) has a group capable of decomposing to generate a polar group by an acid. The repeating unit is a repeating unit having a molar ratio BR1 in the repeating unit of the resin and a group contained in the second resin composition (II) having a group capable of decomposing to generate a polar group under the action of an acid. The molar ratio BR2 of all the repeating units in the resin has the relationship of the following formula (2): Formula (1): -0.6 (MPa) ^1/2 <SP1-SP2 1 (MPa) ^1/2 ; Formula (2): BR1/BR2>1.

[5] The pattern forming method according to any one of [1] to [3] wherein the solubility parameter SP1 of the resin contained in the first resin composition (I) is in the second resin composition (II) The solubility parameter SP2 of the resin to be contained has a relationship of the following formula (3), and a repeating unit having a group capable of decomposing to generate a polar group by an acid in the resin contained in the first resin composition (I). The molar ratio of all the repeating units in the resin is BR1, and the resin contained in the second resin composition (II) has a repeating unit capable of decomposing a group which generates a polar group under the action of an acid to the resin. The molar ratio of all the repeating units is BR2, and the relationship between BR1 and BR2 has the following formula (4): Formula (3): SP1-SP2>1 (MPa) ^1/2 ; Formula (4): BR1/BR2>0.2.

[6] The pattern forming method according to any one of [1] to [5] wherein at least any one of the first resin composition (I) and the second resin composition (II) is capable of being lighted A compound that produces an acid upon irradiation with radiation or radiation.

[7] The pattern forming method according to [6], wherein the second resin composition (II) contains a compound capable of generating an acid upon irradiation with actinic rays or radiation.

[8] The pattern forming method according to any one of [1] to [7] wherein the organic solvent-containing developer contains at least one solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, and a guanamine solvent. And a developer of an organic solvent selected from the group consisting of ether solvents.

[9] A multilayer resist pattern formed by the pattern forming method according to any one of [1] to [8].

[10] A multilayer film for organic solvent development comprising: a first film formed on a substrate by using the first resin composition (I); and a second resin composition different from the resin composition (I) The second film formed on the first film of the object (II).

[11] A method of producing an electronic component, comprising the pattern forming method according to any one of [1] to [8].

[12] An electronic component manufactured by the method of producing an electronic component according to [11].

The invention preferably further comprises the following configurations.

[13] The pattern forming method according to any one of [1] to [8], further comprising at least before the exposing step (iii) or after the exposing step (iii) but before the developing step (iv) Heating step.

[14] The pattern forming method according to [13], wherein the first film has a solubility in the organic solvent contained in the developer after the exposing step (iii) and the heating step is smaller than the second film in the exposing step (iii) and The solubility of the organic solvent after the heating step.

[15] The pattern forming method according to any one of [1] to [8], wherein the first resin composition (I) and the second resin composition (II) are at least One contains a basic compound.

[16] The pattern forming method according to [6] or [7], wherein the second resin composition (II) further contains a basic compound.

[17] The pattern forming method according to any one of [1] to [8], wherein the solvent contained in the second resin composition (II) does not have a hydroxyl group. An alcohol of an oxygen atom, an ester having 7 or more carbon atoms, or an ether having no oxygen atom other than an ether bond.

[18] The pattern forming method according to [3], wherein the resin containing a repeating unit having a group capable of decomposing to generate a polar group by an acid further contains a repeating unit having a lactone structure.

[19] The pattern forming method according to [3] or [18], wherein the resin containing a repeating unit having a group capable of decomposing to generate a polar group under the action of an acid further contains a hydroxyadamantyl group or A resin of a repeating unit of dihydroxyadamantyl.

[20] The pattern forming method according to any one of [1] to [8], wherein the first resin composition (I) and the second resin composition (II) Both are chemically amplified resist compositions for organic solvent development.

[21] The pattern forming method according to any one of [1] to [8], wherein the exposure is exposure to a KrF excimer laser or an ArF excimer laser.

According to the present invention, it is possible to provide a pattern forming method capable of forming a pattern having a good LWR while having a rectangular outline, a multilayer resist pattern formed by the method, a multilayer film for organic solvent development suitable for the pattern forming method, A resist composition, a method of manufacturing an electronic component, and an electronic component which are suitable for the pattern forming method.

Modes for carrying out the invention are described in detail below.

In the description of the present invention, when a group (atomic group) is as described below in the case where a substitution or an unsubstituted is not illustrated, the group encompasses a group having no substituent and a group having a substituent. For example, "alkyl" encompasses not only the unsubstituted alkyl group (unsubstituted alkyl group) but also the alkyl group having a substituent (substituted alkyl group).

In the description of the present invention, the term "actinic rap" or "radiation" means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, and an extreme ultraviolet ray (EUV light). , X-ray or electron beam (EB). Further, in the present invention, "light" means actinic rays or radiation.

In the description of the present invention, "exposure" is not specified unless otherwise indicated It covers only ultraviolet light, extreme ultraviolet light, X-ray, EUV light, or the like, which is exposed to a mercury lamp, represented by an excimer laser, and covers lithography using a particle beam such as an electron beam and an ion beam.

The pattern forming method of the present invention comprises: (i) a step of forming a first film on a substrate by using the first resin composition (I); (ii) using a second resin different from the resin composition (I) a step of forming a second film on the first film by the composition (II); (iii) exposing the multilayer film having the first film and the second film; and (iv) using a developer containing an organic solvent The first film in the exposed multilayer film and the second film are developed to form a negative pattern.

That is, in the present invention, the "negative pattern" has a pattern portion formed by developing the first film and a pattern portion formed by developing the second film.

The pattern forming method of the present invention ensures that a reason for forming a pattern having a good LWR and having a rectangular outline when forming a negative pattern by a developer containing an organic solvent is not readily apparent, but is assumed as follows.

The problem that the pattern easily has an overcut profile is a problem in the negative pattern formation method developed using an organic solvent, which is considered to be attributable to light due to the resist film as it travels in the resist film The light is attenuated and attenuated, and further, when the bottom side of the resist film is approached, the generation of acid is further reduced.

In the present invention, the first film (lower layer) on the bottom side of the multilayer resist film and the second film (upper layer) on the surface layer side of the multilayer resist film are formed of different resin compositions, and it is assumed that this is controlled Between the bottom side and the surface side The solubility of the organic solvent-containing developer is different, and the pattern can be controlled to become rectangular without an overcut profile.

In addition, the above control may also improve the LWR.

For the reason of the above assumption, in order to further suppress the overcut profile formation, the first layer (lower layer) formed of the first resin composition (I) and combined in a multilayer configuration form preferably has a lower solubility for the organic developer than when it is resistant. The solubility of the etchant film on the underside of the resist film for the organic developer when the second resin composition is formed alone. Specific examples of the method for achieving such a solubility relationship with respect to the organic developer between the first resin composition (I) and the second resin composition (II) include the following Examples <a> and <b>.

Example <a>:

In the example <a>, the solubility parameter SP1 of the resin contained in the first resin composition (I) and the solubility parameter SP2 of the resin contained in the second resin composition (II) have the relationship of the following formula (1). And the repetition of a group having a group capable of decomposing under the action of an acid to generate a polar group (hereinafter sometimes simply referred to as "acid-decomposable group") in the resin contained in the first resin composition (I) The unit has a repeating unit having an acid-decomposable group in the resin contained in the repeating unit of the resin and all the repeating units in the resin in the resin contained in the second resin composition (II) The ear has a relationship of the following formula (2) to BR2: Formula (1): -0.6 (MPa) ^1/2 <SP1-SP2 1 (MPa) ^1/2 ; Formula (2): BR1/BR2>1.

In the embodiment <a>, the formula (2) is satisfied, and the formula (2) indicates the first resin. The molar ratio of the repeating unit having an acid-decomposable group in the resin contained in the composition (I) is larger than the molar ratio in the resin contained in the second resin composition (II), and this is regarded as It is prescribed that the solubility of the resin contained in the first resin composition (I) with respect to the organic developer is lower than the solubility of the resin contained in the second resin composition (II). Due to this relationship, as long as the solubility parameter difference (SP1-SP2) is within the range represented by the formula (1), the solubility of the first film (lower layer) can be further lower than that of the second film (upper layer), Further, the overcut profile formation can be further suppressed, so that the LWR can be further improved.

From the viewpoint of further suppressing overcut profile formation and further improving LWR, the formula (1) preferably satisfies the following (1'): Formula (1'): -0.2 (MPa) ^1/2 <SP1-SP2 1 (MPa) ^1/2 .

The upper limit of the formula (2) is not particularly limited but is preferably 3 BR1/BR2.

From the viewpoint of further suppressing overcut contour formation and further improving LWR, the formula (2) preferably satisfies the following (2'): Formula (2'): 2 BR1/BR2 1.1.

Example <b>:

Example <b> is a relationship between the solubility parameter SP1 of the resin contained in the first resin composition (I) and the solubility parameter SP2 of the resin contained in the second resin composition (II) having the following formula (3) The embodiment, and the repeating unit having an acid-decomposable group in the resin contained in the first resin composition (I), the molar ratio BR1 and the second resin composition (II) in terms of all the repeating units in the resin The repeating unit having an acid-decomposable group in the resin contained therein has a relationship of the following formula (4) in terms of all repeating units in the resin: Formula (3): SP1-SP2>1 ( MPa) ^1/2 ; Formula (4): BR1/BR2>0.2.

In the embodiment <b>, the formula (3) is satisfied, and this is considered to specify that the solubility of the resin contained in the first resin composition (I) for the organic developer is lower than that in the second resin composition (II) The solubility of the resin contained. Due to this relationship, the solubility of the first film (lower layer) can be further lowered as long as the formula (4) (formula (4) represents the correlation of the molar ratio with respect to the repeating unit having an acid-decomposable group) The solubility in the second film (upper layer) and the formation of the overcut profile can be further suppressed, so that the LWR can be further improved.

The upper limit of the formula (3) is not particularly limited, but is preferably 2.5. SP1-SP2.

From the viewpoint of further suppressing overcut profile formation and further improving LWR, the formula (3) preferably satisfies the following (3'): Formula (3'): 2 (MPa) ^1/2 SP1-SP2>1 (MPa) ^1/2 .

The upper limit of the formula (4) is not particularly limited but is preferably 2 BR1/BR2.

From the viewpoint of further suppressing overcut contour formation and further improving LWR, the formula (4) preferably satisfies the following (4'): Formula (4'): 1.3 BR1/BR2 0.3.

In the present invention, the resin contained in the resin composition (I) and the resin contained in the resin composition (II) are each preferably, for example, as described later in [Preferred Resin Example (1)] The individual repeating units, the individual repeating units described later in [Preferred Resin Example (2)], and the repeating units appropriately selected in the repeating units described later in [other repeating units] are formed to satisfy In the formula (1) and the formula (2) or the embodiment <b> in the embodiment <a> Formula (3) and Formula (4).

Incidentally, the solubility parameter used in the present invention is by the Okitsu method (Journal of the Adhesion Society of Japan , Vol. 29, No. 5 (1993); Adhesion (Adhesion) ) , 246, vol. 38 (6) (1994)) calculated solubility parameter, and calculated by calculating the molar attraction constant (F) of the individual atomic group (structural unit) of the resin or compound, and The value obtained is divided by the molar volume (V).

The solubility parameter can be calculated by dividing the integrated value of the molar attraction constant (F) of the individual structural units shown in Table 1 by the integrated value of the molar volume (V) according to the following formula: Solubility parameter (SP value) =2.04549 × Σ F / Σ V [(MPa) ^1/2 ].

For example, the case of calculating the SP value of the following repeating unit is described below (Example 1).

Since there is 1 CH ₃ , 1 CH ₂ , 1 C (polymer), and 1 COOH, ΣF=205+132-81.7+373=628.3, and ΣV=31.8+16.5-19.2+24.4=53.5.

Therefore, the SP value = 2.04549 × 628.3/53.5 = 24.02 [(MPa) ^1/2 ].

Regarding the calculation of the SP value of the resin, for example, the case of calculating the SP value of the resin represented by the following formula (Example 2) is described below.

In calculating the SP value of the resin, the ΣF value and the ΣV value of each repeating unit were calculated, and the values were multiplied by the value obtained by the molar ratio in the resin, thereby calculating the ΣF value and the ΣV value of the resin.

Thus, the SP value = 2.04549 × (1652.3 × 0.5 + 1853.1 × 0.1 + 1478.6 × 0.4) / (163.6 × 0.5 + 168.5 × 0.1 + 162.2 × 0.4) = 20.05 [(MPa) ^1/2 ].

The pattern forming method of the present invention may include forming the third film after the second film is formed in the step (ii) but before the exposure step (iii) using the third composition (III) different from the second resin composition (II). And a step of forming a fourth film using the fourth resin composition (IV) different from the third resin composition (III).

In the pattern forming method of the present invention, the developer is preferably a developer containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent. .

The pattern forming method of the present invention preferably further comprises the step of rinsing using a washing solution containing an organic solvent.

The rinsing solution is preferably a rinsing solution containing at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent.

In the case where the resin contained in at least one of the first resin composition (I) and the second resin composition (II) is a resin capable of increasing polarity under the action of an acid to increase solubility to an alkali developer, the present invention The pattern forming method may further include a step of performing development using an alkali developer.

The present invention relates to a multilayer resist pattern.

According to the pattern forming method of the present invention, it is obtained by developing The film (for example, the first film and the second film) develops a multilayer resist pattern of the patterned portion formed.

The present invention relates to a multilayer film for organic solvent development.

The multilayer film (multilayer resist film) for organic solvent development of the present invention includes the first one formed on the substrate by using the first resin composition (I) (hereinafter sometimes simply referred to as "resin composition (I)"). A film; and a second film formed on the first film using a second resin composition (II) different from the resin composition (I) (hereinafter sometimes simply referred to as "resin composition (II)").

The term "organic solvent development" as used herein means the application of at least one step of developing a composition using an organic solvent-containing developer.

The resin composition (I) and the resin composition (II) used in the present invention are described below.

The resin composition (I) and the resin composition (II) according to the present invention are used for negative development (the solubility to the organic solvent developer is lowered upon exposure, thus leaving the exposed area in the form of a pattern and removing the unexposed area Development).

The resin composition (I) and/or the resin composition (II) used in the present invention is preferably preferably a resin containing a polar group which is decomposed by an acid to be described later (i.e., capable of being subjected to an acid) A composition of a resin that produces a polar group to reduce the solubility of the organic solvent developer.

Resin composition (I) and resin composition (II) used in the present invention It may be a resin composition containing a resin having a group capable of decomposing to generate a polar group under the action of an acid described later, and a compound which can be described later to be capable of generating an acid upon irradiation with actinic rays or radiation, so-called A chemically amplified sensitizing ray-sensitive or radiation-sensitive resin composition. The photosensitive ray-sensitive or radiation-sensitive resin composition may contain, in addition to a compound having a group capable of decomposing to generate a polar group by an acid, and a compound which can be described later to generate an acid upon irradiation with actinic rays or radiation. The components. This component will be described later.

In the present invention, the first resin composition (I) is different from the second resin composition (II).

The following description of the first resin composition (I) and the second resin composition (II) can be directly applied to the relationship between the third resin composition (III) and the second resin composition (II) (third resin composition ( III) is different from the second resin composition (II), and is applied to the relationship between the fourth resin composition (IV) and the third resin composition (III) (fourth resin composition (IV) and third resin composition (III) is different).

In the present invention, the resin contained in the resin composition (I) is preferably different from the resin contained in the resin composition (II).

In a preferred embodiment of the present invention, at least one of the resin contained in the resin composition (I) and the resin contained in the resin composition (II) is a preferred resin embodiment described later ( The resin in 1), and the other is the resin in the preferred resin embodiment (2) described later. However, the present invention is not limited thereto, and the resin contained in the resin composition (I) or the resin composition (II) may be composed of appropriately selected individual repeating units described later. Resin. For example, the resin may be each repeating unit described later in [Preferred Resin Example (1)] (for example, a repeating unit containing an aromatic ring described later) and later implemented in [Preferred Resin] A copolymer of each repeating unit (for example, a repeating unit represented by the formula (AAI) described later) described in the example (2)].

The resin (hereinafter sometimes simply referred to as "resin (A)") contained in at least one of the first resin composition (I) and the second resin composition (II) of the present invention preferably has the ability to a resin which decomposes under the action of an acid to form a group of a polar group (hereinafter sometimes simply referred to as "acid-decomposable group") (hereinafter sometimes referred to simply as "acid-decomposable resin"), and the resin is capable of A resin that increases polarity under the action of an acid to lower the solubility of the developer containing the organic solvent.

The resin (A) contained in the resin composition (I) or the resin composition (II) used in the present invention contains, for example, an acid-decomposable group in either or both of a main chain and a side chain of the resin. Resin of the group.

Incidentally, the resin (A) is also a resin capable of increasing the polarity under the action of an acid to increase the solubility to an alkali developer.

[repeating unit having an acid decomposable group]

The acid-decomposable group preferably has a structure in which a polar group is protected by a group capable of decomposing and leaving under the action of an acid.

The polar group is not particularly limited as long as it is a group which is slightly soluble or insoluble in the developer containing the organic solvent, but examples thereof include a carboxyl group and an acidic group (which can be used as a resist in general). a dissociated group of a 2.38 mass% aqueous solution of tetramethylammonium hydroxide in the developer) (such as a sulfonic acid group) And alcoholic hydroxyl groups.

The alcoholic hydroxyl group is a hydroxyl group bonded to the hydrocarbon group, and represents a hydroxyl group other than the hydroxyl group (phenolic hydroxyl group) directly bonded to the aromatic ring, and excludes the α-position through an electron-withdrawing group such as a fluorine atom. A substituted aliphatic alcohol in the form of an acid group (e.g., a fluorinated alcohol group (e.g., hexafluoroisopropanol)). The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa of from 12 to 20.

A preferred group as the acid-decomposable group is a group in which a hydrogen atom of the above group is substituted with a group capable of leaving under the action of an acid.

Examples of the group capable of leaving under the action of an acid include -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), and -C(R ₀₁ )( R ₀₂ ) (OR ₃₉ ).

In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be combined with each other to form a ring.

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group or an alkenyl group.

The alkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a n-butyl group, a second butyl group, and a hexyl group. And 辛基.

The cycloalkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. The monocyclic cycloalkyl group is preferably a cycloalkyl group having a carbon number of 3 to 8, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. The polycyclic cycloalkyl group is preferably a cycloalkyl group having 6 to 20 carbon atoms, and examples thereof include an adamantyl group, a norbornyl group, an isoboronyl group, and an anthracene group. A camphanyl group, a dicyclopentyl group, an α-pinel group, a tricyclodecyl group, a tetracyclododecyl group, and an androstanyl group. Incidentally, at least one carbon atom in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

The aryl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an aryl group having a carbon number of 6 to 10, and examples thereof include a phenyl group, a naphthyl group and an anthracenyl group.

The aralkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an aralkyl group having a carbon number of 7 to 12, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.

The alkenyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.

The ring formed by combining R ₃₆ and R _{37 is} preferably a cycloalkyl group (monocyclic or polycyclic). The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group, and an adamantyl group, A monocyclic cycloalkyl group having a carbon number of 5 to 6 is preferred, and a monocyclic cycloalkyl group having a carbon number of 5 is more preferred.

[Preferred Resin Example (1)]

In a preferred embodiment of the invention, the resin (A) is a resin of the preferred resin embodiment (1) described below.

The resin in the preferred resin embodiment (1) is preferably a resin which is applicable to KrF exposure and which contains a repeating unit having an aromatic ring. The repeating unit having an aromatic ring contains, for example, a repeating unit represented by the formula (VI) described later, a repeating unit represented by the formula (IIB) described later, and a repeating unit having an aromatic group described later.

Preferably, the resin in the resin embodiment (1) is preferably from at least one a repeating unit represented by the following formula (III), a repeating unit represented by the formula (VI) described later, a repeating unit represented by the formula (IIB) described later, and a repeat having an aromatic group described later A repeating unit selected from the group consisting of units and, if necessary, at least one resin composed of repeating units selected from the individual repeating units described later in [other repeating units].

The repeating unit having an acid-decomposable group contained in the resin (A) as the resin in the preferred embodiment (1) is preferably a repeating unit represented by the following formula (III):

In the formula (III), R ₀ represents a hydrogen atom or a linear or branched alkyl group.

R ₁ to R ₃ each independently represent a linear or branched alkyl group or a monocyclic or polycyclic cycloalkyl group.

Two members of R ₁ to R ₃ may be combined to form a monocyclic or polycyclic cycloalkyl group.

The linear or branched alkyl group of R ₀ may have a substituent, and is preferably a linear or branched alkyl group having a carbon number of 1 to 4, and examples thereof include a methyl group, an ethyl group, a n-propyl group, and an isopropyl group. Base, n-butyl, isobutyl and tert-butyl. Examples of the substituent include a hydroxyl group and a halogen atom (for example, a fluorine atom).

R _{0 is} preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

The alkyl group of R ₁ to R ₃ is preferably an alkyl group having a carbon number of 1 to 4, such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, and a tert-butyl group.

The cycloalkyl group of R ₁ to R ₃ is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclononyl group or a tetracyclododecyl group. And adamantyl.

The cycloalkyl group formed by combining two members of R ₁ to R ₃ is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; or a polycyclic cycloalkyl group such as a norbornyl group or a tetracyclic ring. An anthracenyl group, a tetracyclododecyl group, and an adamantyl group are more preferably a monocyclic cycloalkyl group having a carbon number of 5 or 6.

A preferred embodiment is an embodiment wherein R ₁ is methyl or ethyl and R ₂ and R _{3 are} combined to form the above cycloalkyl group.

Each of the above groups may have a substituent, and examples of the substituent include a hydroxyl group, a halogen atom (such as a fluorine atom), an alkyl group (having a carbon number of 1 to 4), a cycloalkyl group (having a carbon number of 3 to 8), and an alkoxy group. a group (having a carbon number of 1 to 4), a carboxyl group and an alkoxycarbonyl group (having a carbon number of 2 to 6). The carbon number is preferably 8 or less.

A particularly preferred embodiment of the repeating unit represented by the formula (III) is an embodiment in which R ₁ , R ₂ and R ₃ each independently represent a linear or branched alkyl group.

In this embodiment, the linear or branched alkyl group of R ₁ , R ₂ and R ₃ is preferably an alkyl group having a carbon number of 1 to 4, and examples thereof include a methyl group, an ethyl group, a n-propyl group, and an iso group. Propyl, n-butyl, isobutyl and tert-butyl.

R _{1 is} preferably a methyl group, an ethyl group, a n-propyl group or a n-butyl group, more preferably a methyl group or an ethyl group, still more preferably a methyl group.

R _{2 is} preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group or an n-butyl group, more preferably a methyl group or an ethyl group, still more preferably a methyl group.

R _{3 is} preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, more preferably methyl, ethyl, isopropyl or isobutyl. More preferably, it is a methyl group, an ethyl group or an isopropyl group.

Specific preferred examples of the repeating unit having an acid-decomposable group are explained below, but the present invention is not limited thereto.

In a specific example, Rx represents a hydrogen atom, CH ₃ , CF ₃ or CH ₂ OH, and Rxa and Rxb each represent an alkyl group having a carbon number of 1 to 4. Z represents a substituent, and when a plurality of Z are present, each Z may be the same or different from all other Z. p represents 0 or a positive integer. Specific examples and preferred examples of Z are the same as specific examples and preferred examples of substituents which may be substituted on each of groups such as R ₁ to R ₃ .

For the repeating unit having an acid-decomposable group contained in the resin (A), one type may be used, or two or more types of repeating units having an acid-decomposable group may be used in combination.

In the resin (A) used in the present invention, a preferred resin is preferred from the viewpoint of enhancing the solubility of the exposed region to the organic developer and maintaining the proper solubility of the unexposed region to enhance the dissolution contrast. The content of the repeating unit having an acid-decomposable group (preferably the repeating unit represented by the formula (III)) in the resin of the embodiment (1) (in the case of containing a plurality of repeating units, in total amount) is a resin Preferably, all of the repeating units in (A) are from 20 mol% to 90 mol%, more preferably from 25 mol% to 85 mol%, still more preferably from 30 mol% to 80 mol%.

The resin (A) may contain a repeating unit represented by the following formula (VI):

In the formula (VI), R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₆₂ may be combined with Ar _{6 to} form a ring, and in this case, R ₆₂ represents an alkylene group.

X ₆ represents a single bond, -COO- or -CONR ₆₄ -. R ₆₄ represents a hydrogen atom or an alkyl group.

L ₆ represents a single bond or an alkyl group.

Ar ₆ represents a divalent aromatic ring group.

Y ₂ means (when n At 2 o'clock, each independently represents a hydrogen atom or a group capable of leaving under the action of an acid. However, at least one Y ₂ represents a group which is capable of leaving under the action of an acid.

n represents an integer from 1 to 4.

Formula (VI) is described in more detail.

The alkyl group of R ₆₁ to R ₆₃ in the formula (VI) is preferably an alkyl group which may have a substituent and has a carbon number of 20 or less, such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group. And a second butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, more preferably an alkyl group having a carbon number of 8 or less.

Preferred examples of the alkyl group contained in the alkoxycarbonyl group are the same as those of the preferred examples of the alkyl group in R ₆₁ to R ₆₃ .

The cycloalkyl group may be monocyclic or polycyclic, and is preferably a monocyclic cycloalkyl group which may have a substituent and has a carbon number of 3 to 8, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.

The halogen atom contains a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among them, a fluorine atom is preferred.

In the case where R ₆₂ represents an alkylene group, the alkylene group is preferably an alkylene group which may have a substituent and has a carbon number of 1 to 8, such as a methylene group, an ethyl group, a propyl group, a butyl group, Stretch out the base and stretch out the sin.

Examples of the alkyl group of R ₆₄ in -CONR ₆₄ - (wherein R ₆₄ represents a hydrogen atom or an alkyl group) represented by X ₆ are the same as those of the alkyl group of R ₆₁ to R ₆₃ .

X _{6 is} preferably a single bond, -COO- or -CONH-, more preferably a single bond or -COO-.

The alkylene group in L ₆ is preferably an alkylene group which may have a substituent and has a carbon number of 1 to 8, such as a methylene group, an exoethyl group, a propyl group, a butyl group, a hexyl group, and a octyl group. The ring formed by combining R ₆₂ and L ₆ is preferably a 5-membered ring or a 6-membered ring.

Ar ₆ represents a divalent aromatic ring group. The divalent aromatic ring group may have a substituent, and preferred examples of the divalent aromatic ring group include a aryl group having a carbon number of 6 to 18, such as a phenyl group, a tolyl group, and an anthranyl group; a divalent aromatic ring group of the ring, such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole .

Examples of the substituent which the above alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group and divalent aromatic ring group may have include an alkyl group, a cycloalkyl group, an aryl group, an amine group, a decylamino group, a ureido group. Amino group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, a decyl group, a decyloxy group, an alkoxycarbonyl group, a cyano group, and a nitro group. The carbon number of the substituent is preferably 8 or less.

n is preferably 1 or 2, more preferably 1.

Each of the n Y ₂ independently represents a hydrogen atom or a group capable of leaving under the action of an acid, and the restriction condition is that at least one of n Y ₂ represents a group capable of leaving under the action of an acid.

Examples of the group Y ₂ capable of leaving under the action of an acid include -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(=O)-OC(R ₃₆ )(R ₃₇ )(R ₃₈ ) , -C(R ₀₁ )(R ₀₂ )(OR ₃₉ ), -C(R ₀₁ )(R ₀₂ )-C(=O)-OC(R ₃₆ )(R ₃₇ )(R ₃₈ ) and -CH( R ₃₆ ) (Ar).

In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, a monovalent aromatic ring group, a group formed by combining an alkyl group with a monovalent aromatic ring group, or an alkene. base. R ₃₆ and R ₃₇ may be combined with each other to form a ring.

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a monovalent aromatic ring group, a group formed by combining an alkyl group and a monovalent aromatic ring group, or an alkenyl group. Ar represents a monovalent aromatic ring group.

The alkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a n-butyl group, a second butyl group, and a hexyl group. And 辛基.

The cycloalkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. The monocyclic cycloalkyl group is preferably a cycloalkyl group having a carbon number of 3 to 8, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. The polycyclic cycloalkyl group is preferably a cycloalkyl group having 6 to 20 carbon atoms, and examples thereof include adamantyl group, norbornyl group, isobornyl group, fluorenyl group, dicyclopentyl group, α-fluorenyl group, Tricyclic fluorenyl, tetracyclododecyl and androstalkyl. Incidentally, a part of the carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

The monovalent aromatic ring group of R ₃₆ to R ₃₉ , R ₀₁ , R ₀₂ and Ar is preferably a monovalent aromatic ring group having a carbon number of 6 to 10, and examples thereof include an aryl group such as a phenyl group or a naphthyl group. And a fluorenyl group; and a divalent aromatic ring group containing a heterocyclic ring such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, Triazole, thiadiazole and thiazole.

The group formed by combining the alkyl group and the monovalent aromatic ring group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an aralkyl group having a carbon number of 7 to 12, and examples thereof include a benzene group. Base, phenethyl and naphthylmethyl.

The alkenyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.

The ring formed by combining R ₃₆ and R ₃₇ with each other may be a single ring or a polycyclic ring. The monocyclic ring is preferably a cycloalkyl structure having a carbon number of 3 to 8, and examples thereof include a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, and a cyclooctane structure. The polycyclic ring is preferably a cycloalkyl structure having a carbon number of 6 to 20, and examples thereof include an adamantane structure, a norbornane structure, a dicyclopentane structure, a tricyclodecane structure, and a tetracyclododecane structure. Incidentally, a part of the carbon atoms in the cycloalkyl structure may be substituted with a hetero atom such as an oxygen atom.

Each of the above groups as R ₃₆ to R ₃₉ , R ₀₁ , R ₀₂ and Ar may have a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an amine group, a decylamino group, a urea group, A urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, a decyl group, a decyloxy group, an alkoxycarbonyl group, a cyano group, and a nitro group. The carbon number of the substituent is preferably 8 or less.

The group Y _{2 which} can be removed by the action of an acid is more preferably a structure represented by the following formula (VI-A):

In the formula, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a monovalent aromatic ring group or a group formed by combining an alkyl group and a monovalent aromatic ring group. .

M represents a single bond or a divalent linking group.

Q represents an alkyl group, a cycloalkyl group which may contain a hetero atom, a monovalent aromatic ring group which may contain a hetero atom, an amine group, an ammonium group, a thiol group, a cyano group or an aldehyde group.

At least two members of Q, M and L ₁ may be combined to form a ring (preferably a 5-membered ring or a 6-membered ring).

The alkyl group as L ₁ and L _{2 is} , for example, an alkyl group having 1 to 8 carbon atoms, and specific preferred examples thereof include a methyl group, an ethyl group, a propyl group, a n-butyl group, a second butyl group, a hexyl group, and an octyl group. .

The cycloalkyl group as L ₁ and L _{2 is} , for example, a cycloalkyl group having a carbon number of 3 to 15, and specific preferred examples thereof include a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

The monovalent aromatic ring group as L ₁ and L ₂ is, for example, an aryl group having 6 to 15 carbon atoms, and specific preferred examples thereof include a phenyl group, a tolyl group, a naphthyl group, and an anthracenyl group.

The group formed by combining the alkyl group and the monovalent aromatic ring group as L ₁ and L ₂ is, for example, an aralkyl group having a carbon number of 6 to 20, such as a benzyl group and a phenethyl group.

Examples of the divalent linking group of M include an alkyl group (e.g., a methylene group, an ethyl group, a propyl group, a butyl group, a hexyl group, a octyl group), a cycloalkyl group (e.g., a cyclopentylene group). a base, a cyclohexyl group, an adamantyl group, an alkenyl group (for example, a vinyl group, a propenyl group, a butenyl group), a divalent aromatic ring group (for example, a phenyl group, a tolyl group, a naphthene group). a group, -S-, -O-, -CO-, -SO ₂ -, -N(R ₀ )-, and a divalent linking group formed by combining a plurality of these members. R ₀ is a hydrogen atom or an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms, and particularly a methyl group, an ethyl group, a propyl group, a n-butyl group, a second butyl group, a hexyl group, an octyl group or the like) ).

Examples of the alkyl group as Q are the same as the examples of the individual groups of L ₁ and L ₂ .

An example of a heterocyclic atom-free aliphatic hydrocarbon ring group and a hetero atom-free monovalent aromatic ring group in a cycloalkyl group which may contain a hetero atom and a monovalent aromatic ring group which may contain a hetero atom (ie, The example of Q) includes the above-mentioned cycloalkyl group as L ₁ and L ₂ and a monovalent aromatic ring group, and its carbon number is preferably from 3 to 15.

Examples of the hetero atom-containing cycloalkyl group and the hetero atom-containing monovalent aromatic ring group include a group having a heterocyclic structure such as thiirane or cyclothiolane. ), thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole and pyrrolidone, but the group is not limited thereto As long as it is a structure generally called a hetero ring (a ring composed of carbon and a hetero atom or a ring composed of a hetero atom).

For a ring which can be formed by combining at least two members of Q, M and L ₁ , there are cases where at least two members of Q, M and L ₁ are combined to form, for example, a propyl or butyl group. Thereby forming a 5-membered ring or a 6-membered ring containing an oxygen atom.

In the formula (VI-A), each group represented by L ₁ , L ₂ , M and Q may have a substituent, and examples of the substituent are contained as R ₃₆ to R ₃₉ , R ₀₁ , R ₀₂ and The above substituent of the substituent substituted on Ar. The carbon number of the substituent is preferably 8 or less.

The group represented by -M-Q is preferably a group having a carbon number of 1 to 30, more preferably a group having a carbon number of 5 to 20.

Specific preferred examples of the repeating unit represented by the formula (VI) are explained below, but the present invention is not limited thereto.

The resin (A) may contain two or more than two of the above repeating units.

The content of the repeating unit is preferably from 5 mol% to 50 mol%, more preferably from 10 mol% to 40 mol%, even more preferably from 15 mol% to all repeating units in the resin (A). 35 moles %.

The resin (A) may contain a repeating unit represented by the following formula (IIB):

In the formula, R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.

X ₄ represents a single bond, -COO- or -CONR ₆₄ -, and R ₆₄ represents a hydrogen atom or an alkyl group.

L ₄ represents a single bond or an alkylene group.

Ar ₄ represents a (n+1)-valent aromatic ring group.

n represents an integer from 1 to 4.

Specific examples of the alkyl group, the cycloalkyl group, the halogen atom and the alkoxycarbonyl group of R ₄₁ , R ₄₂ and R ₄₃ in the formula (IIB) and the substituent which may be substituted on these groups and the formula (VI) Specific examples of individual groups are the same.

The aromatic ring group as Ar ₄ may have a substituent, and preferred examples of the aromatic ring group include a aryl group having a carbon number of 6 to 18, such as a phenyl group, a tolyl group, a naphthyl group, and a stretching group. a mercapto group; and an aromatic ring group containing a heterocyclic ring such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, Thiadiazole and thiazole.

Preferred examples of the substituent on each of the above groups include an alkyl group, an alkoxy group such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, and a butoxy group, and an aryl group. (such as phenyl).

Examples of the alkyl group of R ₆₄ in -CONR ₆₄ - (R ₆₄ represents a hydrogen atom or an alkyl group) represented by X ₄ are the same as those of the alkyl group of R ₆₁ to R ₆₃ .

X _{4 is} preferably a single bond, -COO- or -CONH-, more preferably a single bond or -COO-.

The alkylene group in L ₄ is preferably an alkylene group which may have a substituent and has a carbon number of from 1 to 8, such as a methylene group, an exoethyl group, a propyl group, a butyl group, a hexyl group, and a octyl group.

Ar _{4 is} preferably an extended aryl group which may have a substituent and has a carbon number of 6 to 18, more preferably a phenyl group, a naphthyl group or a phenyl group.

The repeating unit represented by the formula (IIB) preferably has a hydroxystyrene structure. That is, Ar _{4 is} preferably a phenyl group.

Specific examples of the repeating unit represented by the formula (IIB) are explained below, but the present invention is not limited thereto. In each formula, a represents an integer of 0 to 2.

The resin (A) may contain two or more than two of the above repeating units.

The content of the repeating unit is preferably from 5 mol% to 60 mol%, more preferably from 10 mol% to 50 mol%, still more preferably from 20 mol% to more than 50 mol%, more preferably from 10 mol% to more than 20 mol% of the total of the repeating units in the resin (A) 40% by mole.

[repeating unit having an aromatic group]

In the present invention, the resin (A) may contain a repeating unit having an aromatic group, and the repeating unit having an aromatic group may be an aromatic group having a non-phenolic aromatic group.

As used herein, "a repeating unit having a non-phenolic aromatic group" means a repeating unit having no phenolic hydroxyl group, and does not mean a repeating unit containing an aromatic group having a phenolic hydroxyl group, nor does it mean having a derivative derived from a phenolic hydroxyl group. A repeating unit of an aromatic group of a group such as a group in which a phenolic hydroxyl group is protected by a group capable of decomposing and leaving under the action of an acid. Such a repeating unit is sometimes preferred in terms of, for example, solubility in a solvent contained in the resin composition or compatibility with an organic solvent developer (a suitable development rate can be attained) for development.

The aromatic group (such as a non-phenolic aromatic group) may have a substituent and is preferably an aryl group having a carbon number of 6 to 10, and examples thereof include a phenyl group and a naphthyl group.

Examples of the substituent include a straight or branched chain having a carbon number of 1 to 4. An alkyl group, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a halogen atom (such as a fluorine atom), a cyano group, an amine group, a nitro group, and a carboxyl group. Among these substituents, a linear or branched alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms may have a more substituent, and other substitutions Examples of the base include a halogen atom such as a fluorine atom.

The aromatic group (such as a non-phenolic aromatic group) is preferably a phenyl group, and when the phenyl group has a substituent, the substituent is substituted at the 4-position of the phenyl group.

In view of etching resistance, an aromatic group such as a non-phenolic aromatic group is preferably a phenyl group which may have a substituent.

In the present invention, the repeating unit having an aromatic group is preferably a repeating unit represented by the following formula (II):

In the formula (II), R ₀₁ represents a hydrogen atom or a linear or branched alkyl group.

X represents a single bond or a divalent linking group.

Ar represents an aromatic group.

R ₄ represents a single bond or an alkylene group.

Specific examples and preferred examples of the linear or branched alkyl group of R ₀₁ are the same as the specific examples and preferred examples described above for the linear or branched alkyl group of R _{0 in} the formula (III).

X is preferably a divalent linking group. Preferred examples of the divalent linking group include -COO- and -CONH-.

Specific examples and preferred examples of the aromatic group Ar are the same as the specific examples and preferred examples described above with respect to the aromatic group. A preferred embodiment of the aromatic group Ar is a non-phenolic aromatic group.

The alkylene group of R ₄ may have a substituent and is preferably an alkylene group having a carbon number of 1 to 4, and examples thereof include a methylene group, an exoethyl group, and a stretching propyl group. Examples of the substituent which the alkylene group of R ₄ may have include an alkyl group having a carbon number of 1 to 4 and a halogen atom such as a fluorine atom.

The alkylene group of R ₄ may have a substituent which may be combined with a substituent which the aromatic group Ar may have to form a ring, and the group forming the ring contains an alkylene group (e.g., an ethyl group, a propyl group).

In order to impart a preferred glass transition temperature (Tg) to the resin during pattern formation, R _{4 is} preferably a single bond or a methylene group which may be substituted with a substituent.

In the resin (A) used in the present invention, from the viewpoint of enhancing the solubility of the organic region by sufficiently reducing the solubility of the exposed region to the organic developer and maintaining the proper solubility of the unexposed region, and additionally imparting etching resistance From the viewpoint of the content of the repeating unit having an aromatic group (preferably the repeating unit represented by the formula (II)) (in the case of containing a plurality of repeating units, in total amount) in the resin (A) Preferably, all of the repeating units are from 10 mol% to 60 mol%, more preferably from 15 mol% to 50 mol%, still more preferably from 20 mol% to 40 mol%.

[Preferred Resin Example (2)]

In another embodiment of the present invention, the resin (A) is a resin of the preferred resin embodiment (2) described below.

Preferred Resin The resin in the embodiment (2) is preferably a resin which is applicable to ArF exposure and typically contains (meth) acrylate repeating units. The content of the (meth) acrylate repeating unit is usually 50 mol% or more than 50 mol%, preferably 75 mol% or more than 75 mol%, based on all the repeating units in the resin. It is more preferable that all of the repeating units are composed of a (meth) acrylate-based repeating unit.

The resin in the preferred resin embodiment (2) is more preferably selected from the group consisting of at least one repeating unit represented by the following formula (AI) and a repeating unit represented by the formula (AAI) described later. A repeating unit of an acid-decomposable group, and (if necessary) at least one resin composed of repeating units selected from the individual repeating units described later in [other repeating units].

The resin (A) preferably contains a repeating unit having an acid-decomposable group, and preferably the repeating unit of the acid-decomposable group in the resin of the resin example (2) is represented by the following formula (AI). Repeat unit:

In the formula (AI), Xa ₁ represents a hydrogen atom, a methyl group which may have a substituent or a group represented by -CH ₂ -R ₉ . R ₉ represents a hydroxyl group or a monovalent organic group. The monovalent organic group contains, for example, an alkyl group having 5 or less carbon atoms and a mercapto group having 5 or less carbon atoms, and is preferably an alkyl group having 3 or less carbon atoms, more preferably a methyl group. Xa _{1 is} preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

T represents a single bond or a divalent linkage group.

Rx ₁ to Rx ₃ each independently represent an alkyl group (straight or branched chain) or a cycloalkyl group (monocyclic or polycyclic).

Two members of Rx ₁ to Rx ₃ may be combined to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the divalent linking group T include an alkylene group, a -COO-Rt- group, and a -O-Rt- group. In the formula, Rt represents an alkylene group or a cycloalkyl group.

T is preferably a single bond or a -COO-Rt- group, more preferably a single bond. Rt is preferably an alkylene group having a carbon number of 1 to 5, more preferably a -CH ₂ - group, a -(CH ₂ ) ₂ - group or a -(CH ₂ ) ₃ - group.

The alkyl group of Rx ₁ to Rx ₃ is preferably an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl group.

The cycloalkyl group of Rx ₁ to Rx ₃ is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclononyl group or a tetracyclododecyl group. And adamantyl.

The cycloalkyl group formed by combining two members of Rx ₁ to Rx ₃ is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; or a polycyclic cycloalkyl group such as a norbornyl group, four The cyclodecyl group, the tetracyclododecyl group, and the adamantyl group are more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms.

Embodiments in which Rx ₁ is a methyl group or an ethyl group and Rx ₂ and Rx _{3 are} combined to form the above cycloalkyl group are also preferred.

In summary, Rx ₁ to Rx ₃ are each independently preferably a linear or branched alkyl group, and are preferably a linear or branched alkyl group having a carbon number of 1 to 4, and examples thereof include a methyl group, Ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl.

In the case where Rx ₁ to Rx ₃ are each independently a linear or branched alkyl group, Rx _{1 is} preferably a methyl group, an ethyl group, a n-propyl group or an n-butyl group, more preferably a methyl group or an ethyl group. More preferably, it is a methyl group. Rx _{2 is} preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group or an n-butyl group, more preferably a methyl group or an ethyl group, still more preferably a methyl group. Rx _{3 is} preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, more preferably methyl, ethyl, isopropyl or isobutyl. More preferably, it is a methyl group, an ethyl group or an isopropyl group.

In the case where T is a single bond and at the same time Rx ₁ to Rx ₃ are each independently a linear or branched alkyl group (in this case, two members of Rx ₁ to Rx ₃ are not combined to form a cycloalkyl group) The pattern forming method can ensure roughness performance, partial pattern size uniformity, and exposure latitude more, and further suppress a decrease in film thickness (so-called film loss) of the pattern portion formed by exposure.

Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (having a carbon number of 1 to 4), a halogen atom, a hydroxyl group, an alkoxy group (having a carbon number of 1 to 4), a carboxyl group, and an alkoxycarbonyl group ( The carbon number is 2 to 6). The carbon number is preferably 8 or less. In summary, since further enhanced acid decomposition, it contains organic solvents. From the viewpoint of the dissolution contrast of the developer of the agent, the substituent is preferably a group containing no hetero atom such as an oxygen atom, a nitrogen atom and a sulfur atom (for example, preferably an alkyl group substituted with a hydroxyl group), More preferably, it is a group consisting of only a hydrogen atom and a carbon atom, and more preferably a linear or branched alkyl group or a cycloalkyl group.

Specific preferred examples of the repeating unit having an acid-decomposable group are explained below, but the present invention is not limited thereto.

In a specific example, Rx and Xa ₁ each represent a hydrogen atom, CH ₃ , CF ₃ or CH ₂ OH, and Rxa and Rxb each represent an alkyl group having 1 to 4 carbon atoms. Z represents a substituent, and when a plurality of Z are present, each Z may be the same or different from all other Z. P represents 0 or a positive integer. Specific examples and preferred examples of Z are the same as specific examples and preferred examples of substituents which may be substituted on each of groups such as Rx ₁ to Rx ₃ .

It is also preferred that the repeating unit containing an acid-decomposable group in the resin for ArF is a repeating unit represented by the following formula (AAI) capable of decomposing to form a carboxyl group by an acid, and because of this configuration, a pattern The formation method can ensure that the roughness performance (such as line width roughness), the local pattern size uniformity, and the exposure latitude are more excellent, and further suppresses the film thickness reduction (so-called film loss) of the pattern portion formed by development.

In the formula, Xa represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom child.

Ry ₁ to Ry ₃ each independently represent an alkyl group or a cycloalkyl group, and two members of Ry ₁ to Ry ₃ may be combined to form a ring.

Z represents a (n+1)-valent linking group having a polycyclic hydrocarbon structure, and the polycyclic hydrocarbon structure may have a hetero atom as a ring member.

L ₁ and L ₂ each independently represent a single bond or a divalent linking group.

n represents an integer from 1 to 3.

When n is 2 or 3, each L ₂ , each Ry ₁ , each Ry _{2 ,} and each Ry ₃ may be the same as or different from all other L ₂ , Ry ₁ , Ry _2, and Ry _{3 , respectively} .

The alkyl group of Xa may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).

The alkyl group of Xa is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a methylol group, and a trifluoromethyl group, of which a methyl group is preferred.

Xa is preferably a hydrogen atom or a methyl group.

The alkyl group of Ry ₁ to Ry ₃ may be an alkyl group or a branched alkyl group, and is preferably an alkyl group having a carbon number of 1 to 4, such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group or a n-butyl group. Base, isobutyl and tert-butyl.

The cycloalkyl group of Ry ₁ to Ry ₃ is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclononyl group or a tetracyclododecyl group. And adamantyl.

The ring formed by combining two members of Ry ₁ to Ry ₃ is preferably a monocyclic hydrocarbon ring such as a cyclopentane ring and a cyclohexane ring; or a polycyclic hydrocarbon ring such as a norbornane ring or a tetracyclic ring. A decane ring, a tetracyclododecane ring, and an adamantane ring are preferred, and a monocyclic hydrocarbon ring having 5 to 6 carbon atoms is more preferred.

Ry ₁ to Ry ₃ are each independently preferably an alkyl group, more preferably an alkyl group or a branched alkyl group having a carbon number of 1 to 4. Further, the total carbon number of the alkyl group or branched alkyl group as Ry ₁ to Ry ₃ is preferably 5 or less.

Ry ₁ to Ry ₃ each may have a more substituent, and examples of the substituent include an alkyl group (having a carbon number of 1 to 4), a cycloalkyl group (having a carbon number of 3 to 8), a halogen atom, an alkoxy group (carbon number) It is 1 to 4), a carboxyl group, and an alkoxycarbonyl group (having a carbon number of 2 to 6). The carbon number is preferably 8 or less. In summary, the substituent is preferably a group containing no hetero atom (such as an oxygen atom, a nitrogen atom, and a sulfur atom) from the viewpoint of further enhancing the dissolution contrast of the developer containing the organic solvent before and after the acid decomposition ( For example, it is preferably not a hydroxyl group-substituted alkyl group), more preferably a group consisting only of a hydrogen atom and a carbon atom, and still more preferably a linear or branched alkyl group or a cycloalkyl group.

The linking group Z having a polycyclic hydrocarbon structure includes a ring-assembly hydrocarbon ring group and a crosslinked cyclic hydrocarbon ring group, and these groups respectively include a group obtained by removing any (n+1) hydrogen atoms from a ring-combined hydrocarbon ring, and a group obtained by removing any (n+1) hydrogen atoms from a self-crosslinking cyclic hydrocarbon ring group.

Examples of the ring-combined hydrocarbon ring group include a bicyclohexane ring group and a perhydronaphthalene ring group. Examples of the crosslinked cyclic hydrocarbon ring group include a bicyclic hydrocarbon ring group such as a decane ring group, a norbornane ring group, a norbornane ring group, a norbornane ring group, and a bicyclooctane ring group. (eg bicyclo [2.2.2] octane ring group, bicyclo [3.2.1] octane ring group); tricyclic hydrocarbon ring group, such as homobledane ring group, adamantane ring a group, a tricyclo[5.2.1.0 ^2,6 ]nonane ring group and a tricyclo[4.3.1.1 ^2,5 ]undecane ring group; and a tetracyclic hydrocarbon ring group such as a tetracyclic ring [4.4. 0.1 ^2,5 .1 ^7,10 ]dodecane ring group and perhydro-1,4-methylene-5,8-methylenenaphthalene ring group. The crosslinked cyclic hydrocarbon ring group also contains a condensed cyclic hydrocarbon ring group, for example, a condensed ring group obtained by condensing a plurality of 5- to 8-membered cycloalkane ring groups, such as perhydronaphthalene (decahydrogen) Decalin ring group, perhydroindole ring group, perhydrophenanthrene group, perhydroacenaphthene ring group, perhydro anthracene ring group, perhydroindole ring group And a perhydrophenalene ring group.

Preferred examples of the crosslinked cyclic hydrocarbon ring group include a norbornane ring group, an adamantane ring group, a bicyclooctane ring group, and a tricyclo[5,2,1,0 ^2,6 ]decane ring. Group. Among these crosslinked cyclic hydrocarbon ring groups, a norbornane ring group and an adamantane ring group are more preferable.

The linking group having a polycyclic hydrocarbon structure represented by Z may have a substituent. Examples of the substituent which may be substituted on Z include, for example, an alkyl group, a hydroxyl group, a cyano group, a keto group (=O), a decyloxy group, -COR, -COOR, -CON(R) ₂ , -SO ₂ R, - a substituent of SO ₃ R and -SO ₂ N(R) ₂ wherein R represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.

As the substituent which Z may have, an alkyl group, an alkylcarbonyl group, a decyloxy group, -COR, -COOR, -CON(R) ₂ , -SO ₂ R, -SO ₃ R, and -SO ₂ N(R) ₂ It may have a more substituent, and this substituent contains a halogen atom (preferably a fluorine atom).

In the linkage group having a polycyclic hydrocarbon structure represented by Z, it constitutes a plurality of The carbon of the ring (which participates in the ring-forming carbon) can be a carbonyl carbon. Further, as described above, the polycyclic ring may have a hetero atom such as an oxygen atom and a sulfur atom as a ring member.

Examples of the linking group represented by L ₁ and L ₂ include -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO ₂ - an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkyl group (preferably having 3 to 10 carbon atoms), an alkenyl group (preferably having 2 to 6 carbon atoms), and a combination of a plurality of The linking group formed by these members, and the linking group having a total carbon number of 12 or less is preferred.

L _{1 is} preferably a single bond, an alkyl group, a -COO-, -OCO-, -CONH-, -NHCO-, -alkyl-COO-, -alkyl-OCO-, -alkyl-CONH -, -alkyl-NHCO-, -CO-, -O-, -SO ₂ - or -alkyl-O-, more preferably a single bond, an alkyl group, an alkyl group - COO- or - Alkyl-O-.

L _{2 is} preferably a single bond, an alkyl group, a -COO-, -OCO-, -CONH-, -NHCO-, -COO-alkylene-, -OCO-alkylene-,-CONH-alkylene group. -, -NHCO-alkylene-, -CO-, -O-, -SO ₂ -, -O-alkylene- or -O-cycloalkyl-, more preferably a single bond, an alkyl group, -COO-alkylene-, -O-alkylene- or -O-cycloalkyl-.

In the above description, the left-hand side key "-" is intended to be bonded to the ester bond on the main chain side of L ₁ and to the Z in L ₂ , and the right-end key "-" is intended to be bonded to L ₁ Z is bonded to an ester bond in L ₂ which is bonded to a group represented by (Ry ₁ )(Ry ₂ )(Ry ₃ )C-.

Incidentally, L ₁ and L ₂ may be bonded to the same atom constituting a polycyclic ring in Z.

n is preferably 1 or 2, more preferably 1.

Specific examples of the repeating unit represented by the formula (AAI) are explained below, but the present invention is not limited thereto. In a specific example, Xa represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom.

For the repeating unit containing the acid-decomposable group in the resin (A) which is the resin in the preferred resin example (2), one or a combination of two or more acid-containing decomposable groups may be used. Repeat unit.

In the present invention, the resin (A) which is a resin in the preferred resin embodiment (2) preferably contains 50 mol% or more than 50 mol% based on all the repeating units in the resin (in the case of containing various repeats) Unit case, total A repeating unit containing an acid-decomposable group, wherein the molecular weight of an eliminated material produced by decomposing a group capable of decomposing a polar group (acid-decomposable group) under the action of an acid (The molecular weight weighted average value (hereinafter sometimes referred to as "mole average value") obtained by the mole fraction in the case where a plurality of elimination substances are generated is 140 or less. In the case of forming a negative image, the exposed region remains as a pattern, and therefore, by making the erasing substance have a smaller molecular weight, the film thickness of the pattern portion can be prevented from being lowered.

In the present invention, the "eliminating substance produced by decomposing an acid-decomposable group" means a substance corresponding to a group which can be decomposed and removed by an acid and decomposed and eliminated by an acid. For example, in the case of the repeating unit (α) described later (in the example described later, the upper leftmost repeating unit), the erasing substance indicates an alkane generated by decomposition of the third butyl moiety. (H ₂ C=C(CH ₃ ) ₂ ).

In the present invention, from the viewpoint of preventing a decrease in the film thickness of the pattern portion, the molecular weight of the substance to be eliminated which is produced by decomposing the acid-decomposable group (the molar average value in the case of producing a plurality of erasing substances) is Good for 100 or less than 100.

The molecular weight lower limit of the elimination substance produced by decomposing the acid-decomposable group (the average value in the case where a plurality of elimination substances are produced) is not particularly limited, but from the viewpoint that the acid-decomposable group exerts its function. It is to be noted that the lower limit is preferably 45 or more, more preferably 55 or more.

In the present invention, in view of the need to more reliably maintain the film thickness as a pattern portion of the exposed region, the content of the repeating unit containing the acid-decomposable group (in In the case of containing a plurality of repeating units, it is more preferably 60 mol% or more than 60 mol%, more preferably 65 mol% or more than 65 mol%, based on the total amount of all repeating units in the resin. Still more preferably 70% by mole or more than 70% by mole, in the repeating unit containing the acid-decomposable group, the molecular weight of the eliminating substance produced by decomposing the acid-decomposable group is 140 or less 140. The upper limit is not particularly limited, but is preferably 90 mol% or less than 90 mol%, more preferably 85 mol% or less than 85 mol%.

Specific examples of the repeating unit containing an acid-decomposable group are explained below, but the present invention is not limited thereto, and the elimination of the acid-decomposable group in the repeating unit of the acid-decomposable group is eliminated. The molecular weight of the substance is 140 or less.

In a particular example, Xa ₁ represents a hydrogen atom, CH ₃ , CF ₃ or CH ₂ OH.

The total content of the repeating unit containing the acid-decomposable group in the resin (A) as the resin in the preferred resin example (2) is preferably 20 mol% or more based on all the repeating units in the resin (A). 20% by mole, more preferably 30% by mole or more than 30% by mole.

Further, the total content of the repeating unit having an acid-decomposable group is preferably 90% by mole or less than 90% by mole, more preferably 85% by mole or less, based on all the repeating units in the resin (A). %.

In the case where the repeating unit having an acid-decomposable group is a repeating unit represented by the formula (AI) and at the same time, in particular, Rx ₁ to Rx ₃ are each independently a linear or branched alkyl group, represented by the formula (AI) The content of the repeating unit is preferably 45 mol% or more than 45 mol%, more preferably 50 mol% or more than 50 mol%, still more preferably 55 mol%, based on all the repeating units in the resin (A). Or greater than 55% by mole. From the standpoint of forming a good pattern, the upper limit is preferably 90 mol% or less than 90 mol%, more preferably 85 mol% or less than 85 mol%. Within the above range, the pattern forming method can ensure roughness performance, partial pattern size uniformity, and exposure latitude more excellent and further suppress film thickness reduction (so-called film loss) of the pattern portion formed by exposure.

[other repeating units]

The resin (A) may further contain a repeating unit having a lactone structure. The repeating unit having a lactone structure is preferably a repeating unit represented by the following formula (AII):

In the formula (AII), Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group which may have a substituent (the number of carbon atoms is preferably from 1 to 4).

Preferred examples of the substituent which the alkyl group of Rb ₀ may have include a hydroxyl group and a halogen atom. The halogen atom of Rb ₀ contains a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb _{0 is} preferably a hydrogen atom, a methyl group, a methylol group or a trifluoromethyl group, more preferably a hydrogen atom or a methyl group.

Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic cycloalkyl structure, an ether bond, an ester bond, a carbonyl group or a divalent linking group formed by a combination thereof. Ab is preferably a single bond or a divalent linking group represented by -Ab ₁ -CO ₂ -.

Ab ₁ is a linear or branched alkyl group or a monocyclic or polycyclic cycloalkyl group, and is preferably a methylene group, an ethyl group, a cyclohexylene group, an adamantyl group or a norbornyl group.

V represents a group having a lactone structure.

As the group having a lactone structure, any group may be used as long as it has a lactone structure, but a 5-member to 7-membered ring lactone structure is preferred, and is fused to another ring structure to form a bicyclic structure or a spiro structure. The 5-member to 7-membered ring lactone structure is preferred. It is more preferable to contain a repeating unit having a lactone structure represented by any one of the following formulae (LC1-1) to (LC1-17). The lactone structure can be directly bonded to the backbone. Among these lactone structures, (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-8), (LC1-13), and (LC1-14) are preferred. .

The lactone moiety may or may not have a substituent (Rb ₂ ). Preferred examples of the substituent (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a monovalent cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and a carbon number of 2 to 8. An alkoxycarbonyl group, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, and an acid decomposable group. Among these groups, an alkyl group having 1 to 4 carbon atoms, a cyano group, and an acid decomposable group are more preferable. n ₂ represents an integer of 0 to 4. When n ₂ is 2 or more, each substituent (Rb ₂ ) may be the same as or different from all other substituents (Rb ₂ ), and further, a plurality of substituents (Rb ₂ ) may be combined to form a ring.

The repeating unit having a lactone group usually has an optical isomer, and any optical isomer can be used. One optical isomer may be used alone, or a mixture of a plurality of optical isomers may be used. In the case where an optical isomer is mainly used, its optical purity (ee) is preferably 90% or more, more preferably 95% or more.

The resin (A) may or may not contain a repeating unit having a lactone structure, but in the case of containing a repeating unit having a lactone structure, the content of the repeating unit in the resin (A) is preferably in terms of all repeating units. It is from 0.5 mol% to 80 mol%, more preferably from 1 mol% to 75 mol%, still more preferably from 3 mol% to 70 mol%. For this repeating unit, one type may be used, or two or more than two such repeating units may be used in combination. By using a specific lactone structure, pattern resolution can be increased and the rectangular profile can be improved.

Specific examples of the repeating unit having a lactone structure in the resin (A) are explained below, but the present invention is not limited thereto. In the formula, Rx represents H, CH ₃ , CH ₂ OH or CF ₃ .

The resin (A) may contain a repeating unit having an acid group. The acid group includes a carboxyl group, a sulfonylamino group, a sulfonimido group, a bissulfonimide group, and an aliphatic alcohol (for example, a hexafluoroisopropanol group) substituted at the α-position electron withdrawing group, and more preferably contains a repeating unit of a carboxyl group. By means of a repeating unit containing an acid group, for example, in the use of forming a contact hole, the resolution is increased. For a repeating unit having an acid group, the acid group is directly bonded to a repeating unit of the resin main chain (such as propylene) a repeating unit formed by an acid or methacrylic acid), a repeating unit in which an acid group is bonded to a resin main chain via a linking group, and an acid group introduced by using a polymerization initiator or a chain transfer agent containing an acid group during polymerization Repeating units at the end of the polymer chain are preferred. The linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure. The repeating unit formed of acrylic acid or methacrylic acid is more preferable.

Specific examples of the repeating unit having an acid group are explained below, but the present invention is not limited thereto.

In specific examples, Rx represents H, CH _3, CH ₂ OH or CF _3.

The resin (A) may or may not contain a repeating unit having an acid group, but in the case where the resin (A) contains a repeating unit having an acid group, the repeating unit is contained in all the repeating units in the resin (A). It is preferably from 1 mol% to 35 mol%, more preferably from 1 mol% to 30 mol%, still more preferably from 3 mol% to 25 mol%.

The resin (A) may further contain a repeating unit having a hydroxyl group or a cyano group, which is a repeating unit different from the above repeating unit. Due to this repeating unit, the adhesion to the substrate and the affinity for the developer can be enhanced. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and preferably has no acid-decomposable group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted by a hydroxyl group or a cyano group is preferably an adamantyl group, a bisadamantyl group or a norbornyl group, more preferably an adamantyl group. The alicyclic hydrocarbon structure is preferably substituted by a hydroxyl group, and more preferably contains a repeating unit having an adamantyl group substituted with at least one hydroxyl group.

In particular, the resin (A) preferably contains a repeating unit having a hydroxyadamantyl group or a dihydroxyadamantyl group from the viewpoint of limiting the acid diffusion generated. The alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably a partial structure represented by the following formula (VIIa) to formula (VIId), more preferably a partial structure represented by the following formula (VIIa):

In the formulae (VIIa) to (VIIc), R ₂ c to R ₄ c each independently represent a hydrogen atom, a hydroxyl group or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. A structure in which one or both of R ₂ c to R ₄ c is a hydroxyl group and the remainder is a hydrogen atom is preferred. In the formula (VIIa), _{two of} R ₂ c to R ₄ c are a hydroxyl group and the balance is preferably a hydrogen atom.

The repeating unit having a partial structure represented by the formula (VIIa) to the formula (VIId) includes a repeating unit represented by the following formula (AIIa) to formula (AIId):

In the formula (AIIa) to the formula (AIId), R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

R ₂ c to R ₄ c in the formula (Vila) to the formula (VIIc) R ₂ c to R ₄ c have the same meaning.

Specific examples of the repeating unit having a hydroxyl group or a cyano group are explained below, but the present invention is not limited thereto.

The resin (A) may or may not contain a repeating unit having a hydroxyl group or a cyano group, but in the case where the resin (A) contains a repeating unit having a hydroxyl group or a cyano group, the content of the repeating unit is in the resin (A) Preferably, all repeating units are from 1 mol% to 70 mol%, more preferably from 3 mol% to 65 mol%, still more preferably from 5 mol% to 60 mol%.

The resin (A) used in the present invention may further contain a repeating unit having an alicyclic hydrocarbon structure containing no polar group (for example, the above acid group, hydroxyl group or cyano group) and exhibiting no acid decomposability. Due to this repeating unit, the solubility of the resin can be appropriately adjusted when developing using a developer containing an organic solvent. Such a repeating unit comprises a repeating unit represented by the formula (IV):

In the formula (IV), R ₅ represents a hydrocarbon group having at least one cyclic structure and having no polar group.

Ra represents a hydrogen atom, an alkyl group or a -CH ₂ -O-Ra ₂ group, wherein Ra ₂ represents a hydrogen atom, an alkyl group or a fluorenyl group. Ra is preferably a hydrogen atom, a methyl group, a methylol group or a trifluoromethyl group, more preferably a hydrogen atom or a methyl group.

The cyclic structure contained in R ₅ contains a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include a cycloalkyl group having a carbon number of 3 to 12, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; and a cycloalkenyl group having a carbon number of 3 to 12, such as a cyclohexenyl group. . The monocyclic hydrocarbon group is preferably a monocyclic hydrocarbon group having 3 to 7 carbon atoms, more preferably a cyclopentyl group or a cyclohexyl group.

The polycyclic hydrocarbon group contains a cyclic combined hydrocarbon group and a crosslinked cyclic hydrocarbon group. Examples of the cyclic combined hydrocarbon group include a dicyclohexyl group and a perhydronaphthyl group. Examples of the crosslinked cyclic hydrocarbon ring include a bicyclic hydrocarbon ring such as a decane ring, a norbornane ring, a norbornane ring, a norbornane ring, and a bicyclooctane ring (for example, a bicyclo[2.2.2]octane ring, a bicyclo[ 3.2.1] Octane ring); a tricyclic hydrocarbon ring such as a homobrane ring, an adamantane ring, a tricyclo[5.2.1.0 ^2,6 ]decane ring, and a tricyclic ring [4.3.1.1 ^2,5 ] eleven An alkane ring; and a tetracyclic hydrocarbon ring such as a tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodecane ring and a perhydro-1,4-methylene-5,8-methylenenaphthalene ring . The crosslinked cyclic hydrocarbon ring also includes a condensed cyclic hydrocarbon ring, for example, a condensed ring formed by condensing a plurality of 5- to 8-membered cycloalkane rings, such as a perhydronaphthalene (decahydronaphthalene) ring, a perhydroindole ring. , a perhydrophenanthrene ring, a perhydroethane naphthalene ring, a perhydroindene ring, a perhydroindole ring, and a perhydroindole ring.

Preferred examples of the crosslinked cyclic hydrocarbon ring include norbornylalkyl, adamantyl, bicyclooctylalkyl and tricyclo[5,2,1,0 ^2,6 ]fluorenyl. Among these crosslinked cyclic hydrocarbon rings, norbornyl group and adamantyl group are more preferable.

These alicyclic hydrocarbon groups may have a substituent, and preferred examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amine group substituted with a hydrogen atom. The halogen atom is preferably a bromine atom, a chlorine atom or a fluorine atom, and the alkyl group is preferably a methyl group, an ethyl group, a butyl group or a tert-butyl group. The alkyl group may have a more substituent, and the substituent which may be further substituted on the alkyl group includes a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amine group substituted with a hydrogen atom.

Examples of the substituent of the hydrogen atom include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkoxycarbonyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms; the substituted methyl group is preferably a methoxymethyl group, a methoxythiomethyl group, a benzyloxymethyl group or a tert-butoxymethyl group. Or 2-methoxyethoxymethyl; the substituted ethyl group is preferably 1-ethoxyethyl or 1-methyl-1-methoxyethyl; the fluorenyl group preferably has a carbon number of 1 An aliphatic sulfhydryl group of up to 6, such as a decyl group, an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, an isobutyl fluorenyl group, a pentamidine group, and a pentamidine group; and the alkoxycarbonyl group contains, for example, an alkyl group having 1 to 4 carbon atoms. Oxycarbonyl group.

The resin (A) may or may not contain a repeating unit having an alicyclic hydrocarbon structure containing no polar group and exhibiting no acid decomposability, but the resin (A) contains an alicyclic group having no polar group. In the case of a hydrocarbon structure and a repeating unit which does not exhibit acid decomposability, the content of the repeating unit is preferably from 1 mol% to 40 mol%, more preferably 1 mol, based on all repeating units in the resin (A). Ear to 20% by mole.

Specific examples of the repeating unit having an alicyclic hydrocarbon structure containing no polar group and exhibiting no acid decomposability are explained below, but the present invention is not limited thereto. In each formula, Ra represents H, CH ₃ , CH ₂ OH or CF ₃ .

In addition to the above repeating structural unit, the resin (A) used in the composition of the present invention may contain various repeating structural units to achieve control of dry etching resistance, suitability to standard developer, and substrate resistance. Adhesion, resist profile, and the properties typically required for resin compositions such as resolution, heat resistance, and sensitivity.

Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the monomers described below.

Due to such a repeating structural unit, the performance required for the resin used in the composition of the present invention can be subtly controlled, in particular: (1) solubility in a coating solvent; (2) film forming property (glass transition temperature); (3) alkali developability; (4) film loss (selection of hydrophilic, hydrophobic or alkali-soluble groups); (5) adhesion of unexposed areas to the substrate; (6) resistance to dry etching; and the like efficacy.

Examples of the monomer include an additive which is selected from the group consisting of acrylate, methacrylate, acrylamide, methacrylamide, allyl compound, vinyl ether, vinyl ester, styrene, and crotonate. Aggregate unsaturated bond Compound.

In addition to these, an addition polymerizable unsaturated compound copolymerizable with a monomer corresponding to each of the above various repeating structural units can be copolymerized.

In the resin (A) used in the composition of the present invention, the molar ratio of the individual repeating structural units is appropriately set to control the dry etching resistance of the composition, suitability to a standard developer, adhesion to a substrate, and adhesion to a substrate. Properties, resist profile, and the performance typically required for resists (such as resolution, heat resistance, and sensitivity).

The form of the resin (A) used in the present invention may be any of a random type, a block type, a comb type, and a star type. The resin (A) can be synthesized, for example, by radical polymerization, cationic polymerization or anionic polymerization corresponding to an unsaturated monomer of an individual structure. The target resin can also be obtained by polymerizing an unsaturated monomer corresponding to the precursor of the individual structure, followed by a polymer reaction.

The resin (A) used in the present invention can be synthesized by a conventional method such as radical polymerization. Examples of the general synthetic method include: a batch polymerization method in which a monomer substance and an initiator are dissolved in a solvent and a solution is heated to effect polymerization; and a dropping polymerization method, wherein A solution containing a monomer substance and an initiator is added dropwise to the heated solvent over a period of from 1 hour to 10 hours. The dropwise addition polymerization method is preferred. Examples of the reaction solvent include tetrahydrofuran; 1,4-dioxane; ether such as diisopropyl ether; ketone such as methyl ethyl ketone and methyl isobutyl ketone; ester solvent such as ethyl acetate; guanamine solvent , such as dimethylformamide and dimethylacetamide; and a solvent described later capable of dissolving the composition of the present invention, such as propylene glycol monomethyl ether acetate, C Glycol monomethyl ether and cyclohexanone. The polymerization is preferably carried out using the same solvent as that used in the resin composition of the present invention. By using the same solvent, particle generation during storage can be suppressed.

The polymerization is preferably carried out in an inert gas atmosphere such as nitrogen or argon. For the polymerization initiator, a commercially available radical initiator (for example, an azo-based initiator and a peroxide) is used to initiate the polymerization. The radical initiator is preferably an azo-based initiator, and an azo-based initiator having an ester group, a cyano group or a carboxyl group is preferred. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, and 2,2'-azobis(2-methylpropionic acid) dimethyl ester. If necessary, additional initiators are added in portions or fractions. After the reaction is completed, the reaction product is poured into a solvent, and the desired polymer is collected by powder, solid or other recovery methods. The concentration at the time of the reaction is from 5% by mass to 50% by mass, preferably from 10% by mass to 30% by mass, and the reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, more preferably from 60 ° C to 100 ° C.

After the reaction was completed, the reaction solution was cooled to room temperature and purified. Purification can be carried out by a conventional method such as liquid-liquid extraction, in which washing with water or combining the reaction solution with a suitable solvent to remove residual monomer or oligomer component; purification method in a solution state, such as extraction and removal only Ultrafiltration of a polymer having a molecular weight not exceeding a specific value; a reprecipitation method in which a resin solution is added dropwise to a poor solvent to solidify the resin in a poor solvent, thereby removing residual monomers and analogs thereof; and in a solid state The purification method, such as washing the slurry with a poor solvent after separating the resin slurry by filtration. For example, by making the reaction solution slightly soluble or insoluble (poor solvent) and the volume is 10 times or less, preferably 10 times as much as the reaction solution. The solvent was contacted with 5 times to precipitate the resin in a solid form.

If the solvent (precipitating solvent or reprecipitation solvent) used in the operation of precipitating or reprecipitating from the polymer solution is a poor solvent of the polymer, it may be sufficient, and the solvent which can be used may be appropriately selected depending on the kind of the polymer. It is selected from hydrocarbons, halogenated hydrocarbons, nitro compounds, ethers, ketones, esters, carbonates, alcohols, carboxylic acids, water, mixed solvents containing such solvents, and the like.

The amount of the precipitation solvent or the reprecipitation solvent to be used can be appropriately selected by considering the efficiency, the yield, and the like, but generally, the amount is from 100 parts by mass to 10,000 parts by mass per 100 parts by mass of the polymer solution. It is preferably from 200 parts by mass to 2,000 parts by mass, more preferably from 300 parts by mass to 1,000 parts by mass.

The temperature at the time of precipitation or reprecipitation can be appropriately selected by considering efficiency or operability, but the temperature is usually from about 0 ° C to 50 ° C, preferably about room temperature (for example, about 20 ° C to 35 ° C). The precipitation or reprecipitation operation can be carried out by known methods such as batch systems and continuous systems using conventional mixing vessels such as agitation tanks.

The precipitated or reprecipitated polymer is typically subjected to conventional solid-liquid separation, such as filtration and centrifugation, followed by drying and use. It is preferred to use a solvent resistant filter member for filtration under pressure. Drying is carried out at atmospheric pressure or reduced pressure (preferably under reduced pressure) at a temperature of from about 30 ° C to 100 ° C, preferably from about 30 ° C to 50 ° C.

Incidentally, after the resin is precipitated and separated, the resin may be redissolved in a solvent, followed by contact with a solvent of a sparingly soluble resin or an insoluble resin. That is, the following methods can be used: after the radical polymerization is completed, Contacting the polymer with a solvent of a sparingly soluble polymer or an insoluble polymer to precipitate the resin (step a); separating the resin from the solution (step b); redissolving the resin in a solvent to prepare a resin solution A (step c Contacting the resin solution A with a slightly soluble resin or an insoluble resin and having a volume smaller than 10 times (preferably 5 times or less than 5 times) of the resin solution A to precipitate the solid resin (step d); and separating Precipitated resin (step e).

Further, in order to prevent resin aggregation or the like from occurring after the preparation of the composition, for example, as described in JP-A-2009-037108, the synthesized resin may be added to dissolve in a solvent to produce a solution, and The step of heating the solution at 30 ° C to 90 ° C for about 30 minutes to 4 hours.

The weight average molecular weight of the resin (A) used in the composition of the present invention is preferably from 1,000 to 200,000, more preferably from 2,000 to 100,000, still more preferably from 3,000 to 70,000 by the GPC method, depending on the polystyrene. Good for 5,000 to 50,000. When the weight average molecular weight is from 1,000 to 200,000, heat resistance and dry etching resistance can be suppressed from being lowered, and at the same time, film formation properties can be prevented from deteriorating due to weakening of developability or increase in viscosity.

The polydispersity (molecular weight distribution) is usually from 1.0 to 3.0, preferably from 1.0 to 2.6, more preferably from 1.2 to 2.4, still more preferably from 1.4 to 2.2. When the molecular weight distribution satisfies the above range, the resolution and the resist profile are excellent, the side walls of the resist pattern are smooth, and the roughness is improved.

In the resin composition (I) or the resin composition (II) used in the present invention, the content of the resin (A) in the entire composition is preferably from 30% by mass to 99% by mass, more preferably 60% by total solid content. Mass% to 95% by mass.

In the present invention, in the resin solution (I) or the resin solution (II) The resin (A) may be used alone or in combination of a plurality of resins (A).

Further, the resin composition (I) or the resin composition (II) used in the present invention may further contain the resin (A) and an acid-decomposable resin other than the resin (A) (capable of increasing polarity under the action of an acid to lower a resin containing solubility in an organic solvent developer). The acid-decomposable resin other than the resin (A) is an acid-decomposable resin composed of the same repeating unit as the repeating unit which may be contained in the resin (A), and the preferred range of the repeating unit and its in the resin The content is the same as described for the resin (A).

In the case of containing an acid-decomposable resin other than the resin (A), if the total content of the acid-decomposable resin other than the resin (A) and the resin (A) is in the above range, the acid in the composition of the present invention may be The content of the decomposition resin may be sufficient. The mass ratio of the resin (A) to the acid-decomposable resin other than the resin (A) can be appropriately adjusted as long as the effect of the present invention can be successfully provided, but the ratio [resin (A) / in addition to the resin (A) The acid-decomposable resin] is preferably 99.9/0.1 to 10/90, more preferably 99.9/0.1 to 60/40.

The resin composition (I) or the resin composition (II) used in the present invention preferably contains only a resin from the viewpoint of providing high resolution and rectangular profile of the resist pattern and imparting etching resistance during dry etching. (A) as an acid-decomposable resin.

[2] (B) Compounds capable of generating acid upon irradiation with actinic rays or radiation

At least any of the first resin composition (I) for forming the first film and the second resin composition (II) for forming the second film used in the present invention preferably contains (B) capable of using light Produced by ray or radiation An acid compound (hereinafter sometimes referred to as "acid generator").

The second resin composition (II) used in the present invention preferably contains an acid generator, and the second resin composition (II) preferably contains a basic compound described later and an acid generator.

Even as described above, light attenuates as light travels in the resist film and reaches the bottom side of the resist film (for example, micro-machining (such as application using ion implantation in a stepped substrate) When the light near the bottom is weakened, or even when the first resin composition (I) does not contain an acid generator as described later, by incorporating the acid generator into the second resin composition (II) The acid generator may diffuse from the second film (upper layer) to the first layer (lower layer), and image resolution or pattern formation may be achieved. In particular, in the recent stepped substrate, there is an ultra-stepped substrate in which the distance between the steps is much lower than the exposure wavelength. It is difficult to analyze an image on such a stepped substrate by optical exposure alone, but as described above, image resolution or pattern formation can be achieved over optical limitations when utilizing the diffusion of the generated acid.

The first resin composition (I) used in the present invention is preferably free of an acid generator. Even if the first resin composition (I) contains an acid generator, when the basic compound described later is simultaneously incorporated, the diffusibility of the generated acid can be controlled and the rectangularity can be controlled, and this case is a comparison. A good example.

The compound (B) capable of generating an acid upon irradiation with actinic rays or radiation is preferably a compound capable of producing an organic acid upon irradiation with actinic rays or radiation.

The acid generator which can be used may suitably be a photoinitiator for cationic photopolymerization, a photoinitiator for radical photopolymerization, and a light for dye A photo-decoloring agent, a photo-dis coloring agent, a known compound capable of generating an acid upon irradiation with actinic rays or radiation, and used for a microresist or the like. And selected from the mixture.

Examples of the acid generator include a diazonium salt, a phosphonium salt, a phosphonium salt, a phosphonium salt, a sulfonium iminosulfonate, an anthracenesulfonate, a diazodiazine, a dihydrazine, and an o-nitrophenylmethylsulfonate.

Among the acid generators, preferred compounds include compounds represented by the following formula (ZI), formula (ZII), and formula (ZIII):

In the formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.

The organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ has a carbon number of usually 1 to 30, preferably 1 to 20.

Two members of R ₂₀₁ to R ₂₀₃ may be combined to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, a guanamine bond or a carbonyl group. An example of a group formed by combining two members of R ₂₀₁ to R ₂₀₃ includes an alkylene group (e.g., a butyl group, a pentyl group).

Z ^- represents a non-nucleophilic anion.

Examples of the non-nucleophilic anion as Z ^- containing include a sulfonate anion, a carboxylate anion, a sulfonimide anion, a bis(alkylsulfonyl)phosphonium anion, and a tris(alkylsulfonyl)methyl anion. .

The non-nucleophilic anion is an anion having a very low ability to cause a nucleophilic reaction, and this anion can inhibit decomposition by nucleophilic reaction in the molecule with aging. Due to this anion, the aging stability of the resist composition can be improved.

Examples of the sulfonate anion include an aliphatic sulfonate anion, an aromatic sulfonate anion, and a camphorsulfonate anion.

Examples of the carboxylate anion include an aliphatic carboxylate anion, an aromatic carboxylate anion, and an aralkylcarboxylate anion.

The aliphatic sulfonate anion and the aliphatic moiety in the aliphatic carboxylate may be an alkyl group or a cycloalkyl group, but are preferably an alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms, and Examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, decyl, decyl, Undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, Cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, and borneol.

The aromatic group in the aromatic sulfonate anion and the aromatic carboxylate anion is preferably an aryl group having a carbon number of 6 to 14, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

The alkyl group, the cycloalkyl group and the aryl group in the aliphatic sulfonate anion and the aromatic sulfonate anion may have a substituent. Examples of the substituent of the alkyl group, the cycloalkyl group and the aryl group in the aliphatic sulfonate anion and the aromatic sulfonate anion include a nitro group and a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom). , iodine atom), carboxyl group, hydroxyl group, amine group, cyano group, alkoxy group (preferably having 1 to 15 carbon atoms), cycloalkyl group (preferably having 3 to 15 carbon atoms), and aryl group (comparison of carbon number) Preferably, it is 6 to 14), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), a mercapto group (preferably having 2 to 12 carbon atoms), and an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms). , an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon atoms), and an alkylimidosulfonyl group (preferably having 1 to 15 carbon atoms) , an aryloxysulfonyl group (preferably having 6 to 20 carbon atoms), an alkylaryloxysulfonyl group (preferably having 7 to 20 carbon atoms), and a cycloalkylaryloxysulfonyl group (compared to carbon number) It is preferably 10 to 20), an alkoxyalkoxy group (preferably having 5 to 20 carbon atoms), and a cycloalkylalkoxy alkoxy group (preferably having 8 to 20 carbon atoms). The aryl group and the ring structure in each group may further have an alkyl group (preferably having 1 to 15 carbon atoms) or a cycloalkyl group (preferably having 3 to 15 carbon atoms) as a substituent.

The aralkyl group in the aralkylcarboxylate anion is preferably an aralkyl group having a carbon number of 7 to 12, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

The alkyl group, the cycloalkyl group, the aryl group and the aralkyl group in the aliphatic carboxylate anion, the aromatic carboxylate anion, and the aralkylcarboxylate anion may have a substituent. Examples of the substituent include the same halogen atom, alkyl group, cycloalkyl group, alkoxy group, and alkylthio group as in the aromatic sulfonate anion.

Examples of sulfonium imine anions include saccharin anions.

The alkyl group in the bis(alkylsulfonyl) quinone imine anion and the tris(alkylsulfonyl)methyl anion is preferably an alkyl group having 1 to 5 carbon atoms, and examples thereof include a methyl group and an ethyl group. , propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl and neopentyl. Examples of such substituents on the alkyl group include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkoxysulfonyl group, an aryloxysulfonyl group, and a cycloalkylaryloxysulfonyl group, wherein the alkane substituted with a fluorine atom The base is preferred.

Other examples of non-nucleophilic anions containing phosphorus fluoride (e.g., PF ₆ ^-), boron trifluoride (e.g., BF ₄ ^-), and antimony fluoride (e.g., SbF ₆ ^-).

Z ^- The non-nucleophilic anion is preferably substituted at least at the α position of the sulfonic acid with a fluorine atom aliphatic sulfonate anion, a fluorine atom or fluorine atoms substituted aromatic sulfonate anion, an alkyl group via a bis(alkylsulfonyl) quinone imine anion substituted with a fluorine atom or a tris(alkylsulfonyl)methyl anion having an alkyl group substituted with a fluorine atom. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion having 4 to 8 carbon atoms or a benzenesulfonate anion having a fluorine atom, more preferably a nonafluorobutanesulfonate anion or perfluorooctanesulfonate Anion, pentafluorobenzenesulfonate anion or 3,5-bis(trifluoromethyl)benzenesulfonate anion.

The acid generator may be a compound capable of producing a sulfonic acid represented by the following formula (BI). In the case where the acid generator is, for example, a compound represented by the formula (ZI) or the formula (ZII), the aromatic sulfonate anion may be an anion capable of producing an arylsulfonic acid represented by the following formula (BI):

In the formula (BI), Ar represents an aromatic ring and may have a substituent other than a sulfonic acid group and an A group.

p represents 0 or an integer greater than zero.

A represents a group containing a hydrocarbon group.

When p is 2 or greater than 2, each A group may be the same or different from all other A groups.

The formula (BI) is described in detail below.

The aromatic ring represented by Ar is preferably an aromatic ring having a carbon number of 6 to 30, more preferably a benzene ring, a naphthalene ring or an anthracene ring, and still more preferably a benzene ring.

Examples of the substituent which the aromatic ring may have, in addition to the sulfonic acid group and the A group, include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a hydroxyl group, a cyano group, a nitro group, and a carboxyl group. In the case of having two or more than two substituents, at least two substituents may be combined with each other to form a ring.

Examples of the group having a hydrocarbon group represented by A include an alkoxy group, an aryloxy group, an alkylthiooxy group, an arylthiooxy group, an alkoxycarbonyl group, an ethyloxy group, a linear alkyl group, a branched alkane. Alkyl, alkenyl, alkynyl, aryl and anthracenyl.

The hydrocarbon group in the group containing a hydrocarbon group represented by A contains a non-cyclic hydrocarbon group and a cyclic aliphatic group. The carbon number of the hydrocarbon group is preferably 3 or more.

With respect to the A group, the carbon atom adjacent to Ar is preferably a tertiary or quaternary carbon atom.

Examples of the acyclic hydrocarbon group in the A group include an isopropyl group, a tert-butyl group, a third pentyl group, a neopentyl group, a second butyl group, an isobutyl group, an isohexyl group, and a 3,3-dimethyl pentane group. Base and 2-ethylhexyl. The upper limit of the carbon number of the acyclic hydrocarbon group is preferably 12 or less, more preferably 10 or less.

Examples of the cyclic aliphatic group in the A group include a cycloalkyl group, an adamantyl group, a norbornyl group, a borneol group, a decyl group, a decahydronaphthyl group, a tricyclodecyl group, Tetracyclic fluorenyl, camphordithio, dicyclohexyl and decenyl, each group having a substituent. The upper limit of the carbon number of the cyclic aliphatic group is preferably 15 or less, more preferably 12 or less.

In the case where the acyclic hydrocarbon group or the cyclic aliphatic group has a substituent, examples of the substituent include a halogen atom, an alkoxy group, an aryloxy group, an alkylthiooxy group, an arylthiooxy group, an alkoxy group. Carbonyl, ethoxylated, linear alkyl, branched alkyl, cycloalkyl, alkenyl, alkynyl, aryl, hydroxy, carboxy, sulfonate, carbonyl, and cyano.

p represents 0 or an integer greater than 0, and the upper limit thereof is not particularly limited as long as it is a chemically possible number. From the standpoint of suppressing acid diffusion, p is usually from 0 to 5, preferably from 1 to 4, more preferably 2 or 3, and most preferably 3.

In view of inhibition of acid diffusion, the A group is preferably substituted at least in the ortho position relative to the sulfonic acid group, more preferably in the two ortho positions.

The acid generator is preferably a compound capable of producing an acid represented by the following formula (III) or formula (IV) upon irradiation with actinic rays or radiation. The compound capable of producing an acid represented by the following formula (III) or formula (IV) has a cyclic organic group, so that the resolution and the roughness efficiency can be further improved.

The above non-nucleophilic anion may be an anion capable of producing an organic acid represented by the following formula (III) or formula (IV):

In the formula, each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.

R ₁ and R ₂ each independently represent a hydrogen atom, a fluorine atom or an alkyl group.

Each L independently represents a divalent linking group.

Cy represents a cyclic organic group.

Rf represents a group of a fluorine atom.

x represents an integer from 1 to 20.

y represents an integer from 0 to 10.

z represents an integer from 0 to 10.

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The alkyl group preferably has a carbon number of from 1 to 10, more preferably from 1 to 4. Further, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specifically, Xf is preferably a fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ or CH ₂ CH ₂ C ₄ F _{9 is more} preferably a fluorine atom or CF ₃ , and even more preferably both Xf are fluorine atoms.

R ₁ and R ₂ each independently represent a hydrogen atom, a fluorine atom or an alkyl group. The alkyl group may have a substituent (preferably a fluorine atom) and is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group having a substituent of R ₁ and R ₂ include CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ and CH ₂ CH ₂ C ₄ F ₉ , wherein CF _{3 is} preferred.

L represents a divalent linking group. Examples of the divalent linking group include -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, alkylene ( The carbon number is preferably from 1 to 6), the cycloalkyl group (the number of carbon atoms is preferably from 3 to 10), the alkenyl group (the number of carbon atoms is preferably from 2 to 6), and the combination of a plurality of these members. Valence linkage group. Among these groups, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO ₂ -, -COO-alkylene-, -OCO-alkylene- , -CONH-alkylene- and -NHCO-alkylene-preferably, and -COO-, -OCO-, -CONH-, -SO ₂ -, -COO-alkylene- and -OCO-alkylene Base - better.

Cy represents a cyclic organic group. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.

The alicyclic group can be monocyclic or polycyclic. The monocyclic alicyclic group contains, for example, a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. The polycyclic alicyclic group includes, for example, a polycyclic cycloalkyl group such as norbornyl group, tricyclodecyl group, tetracyclodecyl group, tetracyclododecyl group, and adamantyl group. In summary, from the viewpoint of intra-membrane diffusion during the PEB (post-exposure bake) step and improved MEEF (mask error enhancement factor), it has a bulky structure and a carbon number of 7 or more. An alicyclic group of 7 is preferred, such as norbornyl, tricyclodecyl, tetracyclononyl, tetracyclododecyl and adamantyl.

The aryl group can be monocyclic or polycyclic. Examples of aryl groups include phenyl, naphthyl, phenanthryl and anthracenyl. Among these groups, naphthyl is due to the light of 193 nm. It is preferred to have a relatively low absorbance.

The heterocyclic group may be monocyclic or polycyclic, but the polycyclic heterocyclic group may limit acid diffusion to a large extent. Heterocyclyl groups may or may not be aromatic. Examples of the aromatic heterocyclic ring include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocyclic ring having no aromaticity include a tetrahydropyran ring, a lactone ring, and a decahydroisoquinoline ring. The heterocyclic ring in the heterocyclic group is preferably a furan ring, a thiophene ring, a pyridine ring or a decahydroisoquinoline ring. Examples of the lactone ring include the lactone structure exemplified in the above resin (A).

The above cyclic organic group may have a substituent, and examples of the substituent include an alkyl group (which may be a linear or branched chain, preferably having a carbon number of 1 to 12), a cycloalkyl group (which may be monocyclic, polycyclic or A spiro ring preferably has a carbon number of 3 to 20), an aryl group (preferably having 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, a decylamino group, a urethane group, a urea group, and sulfur. Ether group, sulfonamide group and sulfonate group. Incidentally, the carbon constituting the cyclic organic group (involving the ring-forming carbon) may be a carbonyl carbon.

x is preferably from 1 to 8, more preferably from 1 to 4, still more preferably 1. y is preferably from 0 to 4, more preferably 0. z is preferably from 0 to 8, more preferably from 0 to 4.

The group of the fluorine atom represented by Rf contains, for example, an alkyl group having at least one fluorine atom, a cycloalkyl group having at least one fluorine atom, and an aryl group having at least one fluorine atom.

The alkyl group, the cycloalkyl group and the aryl group may be substituted by a fluorine atom or may be substituted by a substituent of another fluorine atom. In the case where Rf is a cycloalkyl group having at least one fluorine atom or an aryl group having at least one fluorine atom, another fluorine-containing The substituent includes, for example, an alkyl group substituted with at least one fluorine atom.

Further, the alkyl group, the cycloalkyl group, and the aryl group may be further substituted with a substituent which does not contain a fluorine atom. Examples of such a substituent include a substituent having no fluorine atom in the substituent described above with respect to Cy.

Examples of the alkyl group having at least one fluorine atom represented by Rf are the same as those described above for the alkyl group substituted by at least one fluorine atom represented by Xf. Examples of the cycloalkyl group having at least one fluorine atom represented by Rf include a perfluorocyclopentyl group and a perfluorocyclohexyl group. Examples of the aryl group having at least one fluorine atom represented by Rf include a perfluorophenyl group.

The organic group represented by R ₂₀₁ , R ₂₀₂ and R ₂₀₃ contains, for example, a corresponding compound (ZI-1), a compound (ZI-2), a compound (ZI-3), and a compound (ZI-4) described later. Group.

The compound may be a compound having a plurality of structures represented by the formula (ZI). For example, the compound may be a compound having a structure in which at least one of R ₂₀₁ to R ₂₀₃ in the compound represented by the formula (ZI) is bonded to the formula (ZI) via a single bond or a bonded group. Another compound of at least one of R ₂₀₁ to R ₂₀₃ .

The compound (ZI-1), the compound (ZI-2), the compound (ZI-3) and the compound (ZI-4) described below are more preferred as the component (ZI).

The compound (ZI-1) is an arylsulfonium compound in which at least one of R ₂₀₁ to R ₂₀₃ in the formula (ZI) is an aryl group, that is, a compound having an arylsulfonium as a cation.

In the arylsulfonium compound, all of R ₂₀₁ to R ₂₀₃ may be an aryl group, or one of R ₂₀₁ to R ₂₀₃ may be an aryl group, and the balance is an alkyl group or a cycloalkyl group.

Examples of the arylsulfonium compound include a triarylsulfonium compound, a diarylalkylsulfonium compound, an aryldialkylsulfonium compound, a diarylcycloalkylsulfonium compound, and an arylbicycloalkylsulfonium compound.

The aryl group in the arylsulfonium compound is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an anthracene residue, a benzofuran residue, and a benzothiophene residue. In the case where the aryl hydrazine compound has two or more than two aryl groups, the two or more aryl groups may be the same or different.

The aryl hydrazine compound preferably has an alkyl group or a cycloalkyl group as a straight or branched alkyl group having a carbon number of 1 to 15 or a cycloalkyl group having a carbon number of 3 to 15, and examples thereof include a methyl group. , ethyl, propyl, n-butyl, t-butyl, t-butyl, cyclopropyl, cyclobutyl and cyclohexyl.

The aryl group, the alkyl group and the cycloalkyl group of R ₂₀₁ to R ₂₀₃ may have the following substituents: an alkyl group (for example, a carbon number of 1 to 15), a cycloalkyl group (for example, a carbon number of 3 to 15), and an aryl group ( For example, the carbon number is 6 to 14), the alkoxy group (for example, the carbon number is 1 to 15), a halogen atom, a hydroxyl group or a phenylthio group. The substituent is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or a linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms. More preferably, it is an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted on any of the three members R ₂₀₁ to R ₂₀₃ or may be substituted on all three members. In the case where R ₂₀₁ to R ₂₀₃ are an aryl group, the substituent is preferably substituted at the para position of the aryl group.

The compound (ZI-2) is described below.

The compound (ZI-2) is a compound in which R ₂₀₁ to R ₂₀₃ in the formula (ZI) each independently represent an organic group having no aromatic ring. An aromatic ring as used herein encompasses an aromatic ring containing a hetero atom.

The organic group having no aromatic ring of R ₂₀₁ to R ₂₀₃ has a carbon number of usually 1 to 30, preferably 1 to 20.

R ₂₀₁ to R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, more preferably a linear or branched 2-sided oxyalkyl group, a 2-sided oxycycloalkyl group or The alkoxycarbonylmethyl group is more preferably a linear or branched 2-sided oxyalkyl group.

The alkyl group of R ₂₀₁ to R ₂₀₃ and the cycloalkyl group are preferably a linear or branched alkyl group having a carbon number of 1 to 10 (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group) and a carbon number of a cycloalkyl group of 3 to 10 (e.g., cyclopentyl, cyclohexyl, norbornyl). The alkyl group is more preferably a 2-sided oxyalkyl group or an alkoxycarbonylmethyl group. The cycloalkyl group is more preferably a 2-sided oxycycloalkyl group.

The 2-sided oxyalkyl group may be a straight chain or a branched chain, and preferably has a group of >C=O at the 2-position of the above alkyl group.

The 2-sided oxycycloalkyl group preferably has a group of >C=O at the 2-position of the above cycloalkyl group.

The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkoxy group having a carbon number of 1 to 5 (e.g., methoxy, ethoxy, propoxy, butoxy, pentyloxy).

R ₂₀₁ to R ₂₀₃ may be further substituted by a halogen atom, an alkoxy group (for example, a carbon number of 1 to 5), a hydroxyl group, a cyano group or a nitro group.

The compound (ZI-3) is described below.

The compound (ZI-3) is a compound represented by the following formula (ZI-3), and It is a compound having a benzamidine methyl phosphonium salt structure.

In the formula (ZI-3), R _1c to R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, A cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group.

R _6c and R _7c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.

R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-sided oxyalkyl group, a 2-sided oxycycloalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group.

Any two or more than two members R _1c to R _5c , a pair of R _5c and R _6c , a pair of R _6c and R _7c , a pair of R _5c and R _x or a pair of R _x and R _y may be combined Together form a ring structure. This ring structure may contain an oxygen atom, a sulfur atom, a ketone group, an ester bond or a guanamine bond.

The above ring structure comprises an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, and a polycyclic fused ring formed by combining two or more than these rings. The ring structure comprises a 3 to 10 member ring and preferably a 4 to 8 member ring, more preferably a 5 or 6 member ring.

Examples of groups formed by combining any two or more than R _1c to R _5c , a pair of R _6c and R _7c or a pair of R _x and R _y include a butyl group and a pentyl group. .

The group formed by combining a pair of R _5c and R _6c or a pair of R _5c and R _x is preferably a single bond or an alkyl group, and examples of the alkyl group include a methylene group and an ethyl group.

Zc ^- represents a non-nucleophilic anion, and an example thereof is the same as an example of a non-nucleophilic anion of Z ^{- in} the formula (ZI).

The alkyl group as R _1c to R _7c may be a straight or branched chain, and is, for example, an alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 12 carbon atoms (for example, A) A propyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, or a linear or branched pentyl group. The cycloalkyl group includes, for example, a cycloalkyl group having a carbon number of 3 to 10 (e.g., a cyclopentyl group, a cyclohexyl group).

The aryl group as R _1c to R _5c is preferably an aryl group having a carbon number of 5 to 15, and examples thereof include a phenyl group and a naphthyl group.

The alkoxy group as R _1c to R _5c may be a straight chain, a branched chain or a cyclic chain, and is, for example, an alkoxy group having a carbon number of 1 to 10, preferably a linear or branched chain having a carbon number of 1 to 5. Alkoxy (for example methoxy, ethoxy, linear or branched propoxy, linear or branched butoxy, or linear or branched pentyloxy), or a carbon number of 3 to 10 A cyclic alkoxy group (e.g., cyclopentyloxy or cyclohexyloxy).

As specific examples of the alkoxycarbonyl group of R _1c to R _5c are the same as specific examples of the alkoxy group and of R _1c to R _5c alkoxy.

Specific examples of the alkylcarbonyloxy group of R _1c to R _5c and the alkyl group of the alkylthio group are the same as the specific examples of the alkyl group of R _1c to R _5c .

As specific examples of R _1c to R _5c Cycloalkylcarbonyloxy in the specific example of a cycloalkyl group with R _1c to R _5c is the same as the cycloalkyl group.

As R _1c to R _5c, and specific examples of the aryloxy group in the arylthio group and the aryl group Specific examples of R _1c to R _5c is the same as the aryl group.

A compound of any one of R _1c to R _5c is a linear or branched alkyl group, a cycloalkyl group or a linear, branched or cyclic alkoxy group, and the sum of carbon numbers of R _1c to R _5c is Compounds from 2 to 15 are more preferred. Due to such a compound, solvent solubility can be further improved and particle generation during storage can be suppressed.

The ring structure which can be formed by combining any two or more than two members of R _1c to R _5c with each other is preferably a 5-membered or 6-membered ring, more preferably a 6-membered ring (such as a phenyl ring).

A ring structure which can be formed by combining R _5c and R _6c with each other includes a carbonyl carbon atom by combining R _5c and R _6c with each other to form a single bond or an alkyl group such as a methylene group or an ethyl group. And a 4-membered ring or a ring of more than 4 members formed by the carbon atoms in the formula (ZI) (preferably a 5-membered ring or a 6-membered ring).

The aryl group as R _6c and R _7c is preferably an aryl group having a carbon number of 5 to 15, and examples thereof include a phenyl group and a naphthyl group.

An embodiment in which both R _6c and R _7c are alkyl groups, and R _6c and R _7c are each a straight or branched alkyl group having a carbon number of 1 to 4, and both are preferred. The basis of the embodiment is even better.

In the case where R _6c and R _{7c are} combined to form a ring, the group formed by combining R _6c and R _7c is preferably an alkylene group having a carbon number of 2 to 10, and examples thereof include an ethyl group and a stretching group. Base, butyl, pentyl and hexyl. Further, a ring formed by combining R _6c and R _7c may contain a hetero atom such as an oxygen atom in the ring.

Examples of the alkyl group as R _x and R _y and the cycloalkyl group are the same as the examples of the alkyl group in R _1c to R _7c and the cycloalkyl group.

Examples of the 2-sided oxyalkyl group and the 2-sided oxycycloalkyl group of R _x and R _y include a group having >C=O at the 2-position of the alkyl group or the cycloalkyl group as R _1c to R _7c . group.

Examples of the alkoxy group in the alkoxycarbonylalkyl group of R _x and R _y are the same as the examples of the alkoxy group in R _1c to R _5c . The alkyl group is, for example, an alkyl group having 1 to 12 carbon atoms, preferably a linear alkyl group having a carbon number of 1 to 5 (e.g., methyl or ethyl).

The allyl group as R _x and R _y is not particularly limited, but is preferably an unsubstituted allyl group or a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having a carbon number of 3 to 10). ) substituted allyl.

The vinyl group as R _x and R _y is not particularly limited, but is preferably an unsubstituted vinyl group or a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having a carbon number of 3 to 10). Vinyl.

A ring structure which can be formed by combining R _5c and R _x with each other includes a formula (I) by combining R _5c and R _x with each other to form a single bond or an alkyl group such as a methylene group or an ethyl group. a ring of 5 or more members (preferably a 5-membered ring) formed by a sulfur atom and a carbonyl carbon atom.

The ring structure which can be formed by combining R _x and R _y with each other contains a divalent R _x and R _y (for example, a methylene group, an ethyl group or a propyl group) and a sulfur atom in the formula (ZI-3). The 5-member or 6-membered ring formed together is preferably a 5-membered ring (i.e., a tetrahydrothiophene ring).

R _x and R _y are each preferably an alkyl group or a cycloalkyl group having a carbon number of 4 or more, more preferably 6 or more, still more preferably 8 or more.

R _1c to R _7c , R _x and R _y each may have a more substituent, and examples of such a substituent include a halogen atom (e.g., a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group. , aryl, alkoxy, aryloxy, decyl, arylcarbonyl, alkoxyalkyl, aryloxyalkyl, alkoxycarbonyl, aryloxycarbonyl, alkoxycarbonyloxy and aryloxy Alkoxy group.

In the above formula (ZI-3), more preferably, R _1c , R _2c , R _4c and R _5c each independently represent a hydrogen atom, and R _3c represents a group other than a hydrogen atom, that is, an alkane Base, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, halogen atom, hydroxy, nitro, alkylthio or arylthio .

Examples of the cation used in the compound (ZI-2) or the compound (ZI-3) of the present invention include paragraphs [0130] to [0134] of JP-A-2010-256842 and JP-A-2011-76056 [ 0136] to the cation described in paragraph [0140].

The compound (ZI-4) is described below.

The compound (ZI-4) is represented by the following formula (ZI-4):

In the formula (ZI-4), R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group or a group having a cycloalkyl group. These groups may have a substituent.

When a plurality of R ₁₄ are present, each R ₁₄ independently represents hydroxy, alkyl, cycloalkyl, alkoxy, alkoxycarbonyl, alkylcarbonyl, alkylsulfonyl, cycloalkylsulfonyl or a group of a cycloalkyl group. These groups may have a substituent.

Each R ₁₅ independently represents an alkyl group, a cycloalkyl group or a naphthyl group. The two R ₁₅ can be combined with each other to form a ring. These groups may have a substituent.

l represents an integer from 0 to 2.

r represents an integer from 0 to 8.

Z ^- represents a non-nucleophilic anion, and an example thereof is the same as an example of a nucleophilic anion of Z ^{- in} the formula (ZI).

In the formula (ZI-4), the alkyl group of R ₁₃ , R ₁₄ and R ₁₅ is a linear or branched alkyl group having a carbon number of preferably 1 to 10, and preferred examples thereof include a methyl group, an ethyl group, N-butyl and tert-butyl.

The cycloalkyl group of R ₁₃ , R ₁₄ and R ₁₅ includes a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having a carbon number of 3 to 20), and particularly preferably a cyclopropyl group, a cyclopentyl group, Cyclohexyl, cycloheptyl or cyclooctyl.

The alkoxy group of R ₁₃ and R ₁₄ is a linear or branched alkoxy group having a carbon number of preferably 1 to 10, and preferred examples thereof include a methoxy group, an ethoxy group, a n-propoxy group and a n-butoxy group. base.

The alkoxycarbonyl group of R ₁₃ and R ₁₄ is a linear or branched alkoxycarbonyl group having a carbon number of preferably 2 to 11, and preferred examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group and a n-butoxy group. Carbonyl.

The group having a cycloalkyl group of R ₁₃ and R ₁₄ includes a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having a carbon number of 3 to 20), and examples thereof include a monocyclic or polycyclic cycloalkoxy group. And an alkoxy group having a monocyclic or polycyclic cycloalkyl group. These groups may have more substituents.

The monocyclic or polycyclic cycloalkoxy group of R ₁₃ and R ₁₄ preferably has a total carbon number of 7 or more, more preferably 7 to 15 total carbon atoms, and preferably has a monocyclic cycloalkyl group. The monocyclic cycloalkoxy group having a total carbon number of 7 or more represents a monocyclic cycloalkoxy group such as a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group or a cycloheptyloxy group. a cyclooctyloxy group and a cycloalkoxy group of a cyclododecyloxy group optionally having a substituent such as an alkyl group (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl) , dodecyl, 2-ethylhexyl, isopropyl, t-butyl, tert-butyl, isopentyl), hydroxyl, halogen atom (eg fluorine, chlorine, bromine, iodine), nitro, cyanide Alkyl, amidino, sulfonylamino, alkoxy (eg methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, butoxy), alkoxycarbonyl (eg A An oxycarbonyl group, an ethoxycarbonyl group, a fluorenyl group (for example, a decyl group, an ethyl fluorenyl group, a benzhydryl group), a decyloxy group (for example, an ethoxy group, a butyloxy group), and a carboxyl group, and a ring thereof The total carbon number, including the carbon number of any substituent on the alkyl group, is 7 or more.

Further, examples of the polycyclic cycloalkoxy group having a total carbon number of 7 or more include a norbornyloxy group, a tricyclodecyloxy group, a tetracyclodecyloxy group, and an adamantyloxy group.

The alkoxy group having a monocyclic or polycyclic cycloalkyl group of R ₁₃ and R ₁₄ preferably has a total carbon number of 7 or more, more preferably a total carbon number of 7 to 15, and preferably has a monocyclic ring. Alkoxy group of alkyl. The alkoxy group having a total carbon number of 7 or more and having a monocyclic cycloalkyl group means an alkoxy group in which the above monocyclic cycloalkyl group which may have a substituent is substituted on an alkoxy group, the alkoxy group For example, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, dodecyloxy, 2-ethylhexyloxy, isopropyl The oxy group, the second butoxy group, the third butoxy group, and the isopentyloxy group, and the total carbon number including the carbon number of the substituent is 7 or more. Examples thereof include a cyclohexylmethoxy group, a cyclopentylethoxy group, and a cyclohexylethoxy group, of which a cyclohexylmethoxy group is preferred.

Examples of the alkoxy group having a total carbon number of 7 or more and having a polycyclic cycloalkyl group include a norbornylalkylmethoxy group, a norbornylalkylethoxy group, a tricyclodecylmethoxy group, and a tricyclodecyl group. Ethoxy, tetracyclodecylmethoxy, tetracyclodecylethoxy, adamantylmethoxy, and adamantylethoxy, wherein norbornyl alkyl methoxy and norbornyl ethoxy Preferably.

Specific examples of the alkyl group in the alkylcarbonyl group of R ₁₄ are the same as those of the alkyl group of R ₁₃ to R ₁₅ .

The alkylsulfonyl or cycloalkylsulfonyl group of R ₁₄ is a linear, branched or cyclic alkylsulfonyl group having a carbon number of preferably 1 to 10, and preferred examples thereof include a methanesulfonyl group, Ethylsulfonyl, n-propanesulfonyl, n-butanesulfonyl, cyclopentanesulfonyl and cyclohexanesulfonyl.

Examples of the substituent which each of the above groups may have include a halogen atom (e.g., a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxycarbonyloxy group. base.

Examples of the alkoxy group include a linear, branched or cyclic alkoxy group having a carbon number of 1 to 20, such as a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, and 2 -methylpropoxy, 1-methylpropoxy, tert-butoxy, cyclopentyloxy and cyclohexyloxy.

Examples of the alkoxyalkyl group include a linear, branched or cyclic alkoxyalkyl group having a carbon number of 2 to 21, such as a methoxymethyl group, an ethoxymethyl group, a 1-methoxyethyl group, 2-methoxyethyl, 1-ethoxyethyl and 2-ethoxyethyl.

Examples of the alkoxycarbonyl group include a linear, branched or cyclic alkoxycarbonyl group having a carbon number of 2 to 21, such as a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an isopropoxycarbonyl group, N-Butoxycarbonyl, 2-methylpropoxycarbonyl, 1-methylpropoxycarbonyl, tert-butoxycarbonyl, cyclopentyloxycarbonyl and cyclohexyloxycarbonyl.

Examples of the alkoxycarbonyloxy group include a linear, branched or cyclic alkoxycarbonyloxy group having a carbon number of 2 to 21, such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, or a n-propoxy group. A carbonyloxy group, an isopropoxycarbonyloxy group, a n-butoxycarbonyloxy group, a tert-butoxycarbonyloxy group, a cyclopentyloxycarbonyloxy group, and a cyclohexyloxycarbonyloxy group.

A ring structure which can be formed by combining two R ₁₅ with each other comprises a 5-member or 6-membered ring formed by two R ₁₅ and a sulfur atom in the formula (ZI-4), preferably a 5-membered ring (also That is, a tetrahydrothiophene ring), and may be fused to an aryl group or a cycloalkyl group. The divalent R ₁₅ may have a substituent, and examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxy group. Carbonyloxy. For substituents on the ring structure, a plurality of substituents may be present, and they may be combined with each other to form a ring (aromatic or non-aromatic hydrocarbon ring, aromatic or non-aromatic heterocyclic ring or by combining two or more than two a polycyclic condensed ring formed by these rings).

In the formula (ZI-4), R _{15 is} preferably, for example, a methyl group, an ethyl group, a naphthyl group or a divalent group capable of forming a tetrahydrothiophene ring structure together with a sulfur atom when the two R ₁₅ groups are combined.

The substituent which may be substituted on R ₁₃ and R ₁₄ is preferably a hydroxyl group, an alkoxy group, an alkoxycarbonyl group or a halogen atom (particularly a fluorine atom).

l is preferably 0 or 1, more preferably 1.

r is preferably from 0 to 2.

Examples of the cations in the compound represented by the formula (ZI-4) used in the present invention include JP-A-2010-256842, paragraph [0121], paragraph [0123], and paragraph [0124], and JP-A-2011-76056. The cations described in paragraph [0127], paragraph [0129], and paragraph [0130].

Formula (ZII) and Formula (ZIII) are described below.

In the formula (ZII) and the formula (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group.

The aryl group of R ₂₀₄ to R ₂₀₇ is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group of R ₂₀₄ to R ₂₀₇ may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the framework of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, anthracene, benzofuran, and benzothiophene.

The alkyl or cycloalkyl group in R ₂₀₄ to R ₂₀₇ is preferably a linear or branched alkyl group having a carbon number of 1 to 10 (e.g., methyl, ethyl, propyl, butyl, pentyl) or a carbon number. It is a cycloalkyl group of 3 to 10 (e.g., cyclopentyl, cyclohexyl, norbornyl).

The aryl group, the alkyl group and the cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have a substituent. Examples of the substituent which the aryl group, the alkyl group and the cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have include an alkyl group (for example, a carbon number of 1 to 15), a cycloalkyl group (for example, a carbon number of 3 to 15), and an aryl group. (for example, a carbon number of 6 to 15), an alkoxy group (for example, a carbon number of 1 to 15), a halogen atom, a hydroxyl group, and a phenylthio group.

Z ^- represents a non-nucleophilic anion, and an example thereof is the same as an example of a non-nucleophilic anion of Z ^{- in} the formula (ZI).

Other examples of the acid generator include a compound represented by the following formula (ZIV), formula (ZV), and formula (ZVI):

In the formula (ZIV) to the formula (ZVI), Ar ₃ and Ar ₄ each independently represent an aryl group.

R ₂₀₈ , R ₂₀₉ and R ₂₁₀ each independently represent an alkyl group, a cycloalkyl group or an aryl group.

A represents an alkyl group, an alkenyl group or an aryl group.

Specific examples of the aryl group of Ar ₃ , Ar ₄ , R ₂₀₈ , R ₂₀₉ and R ₂₁₀ are the same as the specific examples of the aryl group of R ₂₀₁ , R ₂₀₂ and R _{203 in} the formula (ZI-1).

Specific examples of the alkyl group of R ₂₀₈ , R ₂₀₉ and R ₂₁₀ and the cycloalkyl group are the same as the specific examples of the alkyl group of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ and the cycloalkyl group in the formula (ZI-2).

The alkyl group of A contains an alkylene group having a carbon number of 1 to 12 (e.g., methylene, ethyl, propyl, isopropyl, butyl, isobutyl); An alkenyl group having 2 to 12 carbon atoms (for example, a vinyl group, a propenyl group, a butenyl group); and a aryl group having a carbon number of 6 to 10 (for example, a phenyl group, Stretching tolyl, stretching naphthyl).

Among the acid generators, the compound represented by the formula (ZI) to the formula (ZIII) is more preferable.

Further, the acid generator is preferably a compound which produces an acid having a sulfonic acid group or a quinone imine group, more preferably a compound which produces a monovalent perfluoroalkanesulfonic acid, and a group which generates a monovalent fluorine atom or a fluorine atom. a compound of an aromatic sulfonic acid or a compound which produces an imide acid substituted with a monovalent fluorine atom or a fluorine atom-containing group, more preferably a fluorine-substituted alkanesulfonic acid or a fluorine-substituted benzenesulfonate. An acid, a fluorine-substituted imidic acid or a fluorine-substituted methion acid salt of a method acid. In particular, the acid generator which can be used is preferably a compound which produces a fluorine-substituted alkanesulfonic acid, a fluorine-substituted benzenesulfonic acid or a fluorine-substituted imidic acid, wherein the acid produced has a pKa of -1. Or less than -1, and in this case, the sensitivity is enhanced.

Particularly preferred examples of the acid generator are explained below.

The acid generator can be synthesized by a known method, for example, it can be synthesized according to the method described in JP-A-2007-161707.

For the acid generator, one type may be used alone or two or more types of acid generators may be used in combination.

The content of the compound capable of generating an acid upon irradiation with actinic rays or radiation in the composition (I) or the composition (II) is preferably 0.1 based on the total solid content of the resin composition (I) or the resin composition (II). The mass% to 30% by mass, more preferably 0.5% by mass to 25% by mass, still more preferably 3% by mass to 20% by mass, still more preferably 3% by mass to 15% by mass.

Further, in the case where the acid generator is represented by the formula (ZI-3) or the formula (ZI-4), the content thereof is preferably 5% by mass based on the total solid content of the composition (I) or the composition (II). 35 mass%, more preferably 8 mass% to 30 mass%, still more preferably 9 mass% to 30 mass%, still more preferably 9 mass% to 25% by mass.

[3] (C) solvent

Examples of the solvent which can be used in the preparation of the resin composition (I) or the resin composition (II) of the present invention include an organic solvent such as an alkylene glycol monoalkyl ether carboxylate or an alkylene glycol monoalkyl ether. An alkyl lactate, an alkyl alkoxypropionate, a cyclic lactone (preferably having a carbon number of 4 to 10), a monoketone compound which may contain a ring (preferably having a carbon number of 4 to 10), an alkylene carbonate, Alkoxyacetic acid alkyl esters and alkyl pyruvates.

Specific examples of such solvents include the solvents described in paragraphs [0441] to [0455] of U.S. Patent Application Publication No. 2008/0187860.

In the present invention, a mixed solvent prepared by mixing a solvent having a hydroxyl group in a structure and a solvent containing no hydroxyl group can be used as the organic solvent.

The hydroxyl group-containing solvent and the hydroxyl group-free solvent may be appropriately selected from the compounds exemplified above, but the hydroxyl group-containing solvent is preferably an alkanediol monoalkyl ether, an alkyl lactate or the like, more preferably Propylene glycol monomethyl ether (propylene glycol monomethyl ether, PGME, another name: 1-methoxy-2-propanol) or ethyl lactate. The solvent containing no hydroxyl group is preferably an alkylene glycol monoalkyl ether acetate, an alkoxypropionic acid alkyl ester, a ring-containing monoketone compound, a cyclic lactone, an alkyl acetate or the like, more preferably Propylene glycol monomethyl ether acetate (PGMEA, another name: 1-methoxy-2-ethoxypropane), ethyl ethoxypropionate, 2-heptanone, γ- Butyrolactone, cyclohexanone or butyl acetate, and most preferably propylene glycol monomethyl ether acetate, ethyl ethoxy propionate or 2-heptanone.

The mixing ratio (by mass) of the hydroxyl group-containing solvent to the hydroxyl group-free solvent is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 60/40. In view of coating uniformity, a mixed solvent having a ratio of a solvent containing no hydroxyl group of 50% by mass or more than 50% by mass is particularly preferable.

The solvent preferably contains propylene glycol monomethyl ether acetate, and is preferably a solvent containing only propylene glycol monomethyl ether acetate or a mixed solvent of two or more solvents containing propylene glycol monomethyl ether acetate.

In the present invention, from the viewpoint of preventing mutual mixing at the interface between the first film and the second film, in a preferred embodiment, the second resin composition for forming the second film (II) The solvent contained in the solvent is an alcohol having no oxygen atom other than the hydroxyl group, an ester having 7 or more carbon atoms, or an ether having no oxygen atom other than the ether bond.

Each of these specific solvents has an appropriate polarity so that mutual mixing can be prevented by dissolving the individual solid contents in the second resin composition (II) after the film formation instead of dissolving the first film.

Particularly preferred is a second resin composition for forming a second film The solvent contained in (II) is an alcohol having no oxygen atom other than a hydroxyl group, an ester having 7 or more carbon atoms, or an ether having no oxygen atom other than an ether bond, and at the same time, is used for forming a first film. The resin contained in the first resin composition (I) is a resin composed of (meth) acrylate repeating units (preferably, all repeating units are composed of (meth) acrylate repeating units) .

The alcohol having no oxygen atom other than the hydroxyl group is preferably a monohydric alcohol having no oxygen atom other than the hydroxyl group. The carbon number of the alcohol having no oxygen atom other than the hydroxyl group is preferably from 1 to 20, more preferably from 3 to 15, still more preferably from 4 to 12, still more preferably from 5 to 10. A specific example of the alcohol comprises 4-methyl-2-pentanol.

The ester having a carbon number of 7 or more is preferably an ester having a carbon number of 7 or more and having no oxygen atom except for one ester bond. The carbon number of the ester having 7 or more carbon atoms is preferably 7 to 20, more preferably 7 to 15, still more preferably 7 to 12, still more preferably 7 to 10. A specific example of the ester comprises isobutyl isobutyrate.

Examples of the ether having no oxygen atom other than the ether bond include a dialkyl ether and an alkyl aryl ether. The carbon number of the ether having no oxygen atom other than the ether bond is preferably from 3 to 20, more preferably from 4 to 15, still more preferably from 5 to 12. A specific example of the ether comprises diisoamyl ether.

The ratio of such a solvent is preferably 30% by mass or more, more preferably 50% by mass or more, more preferably 50% by mass or more, based on all the solvents contained in the second resin composition (II). It is 80% by mass or more than 80% by mass.

[4] (D) Basic compounds

At least one of the first resin composition (I) and the second resin composition (II) used in the present invention preferably contains (D) a basic compound, and the second The resin composition (II) preferably contains (D) a basic compound.

Even when the first resin composition (I) contains the above acid generator, the embodiment in which the (D) basic compound is incorporated into the first resin composition (I) is also one of preferred embodiments because it can be prevented The acid produced diffuses and can control the squareness.

The basic compound is preferably a compound having a structure represented by the following formula (A) to formula (E):

In the formula (A) and the formula (E), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and each represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), and a cycloalkyl group (carbon number ratio). Preferably, it is 3 to 20) or an aryl group (carbon number is 6 to 20), and R ²⁰¹ and R ²⁰² may be combined to form a ring. R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.

With respect to the alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms or a cyanoalkyl group having 1 to 20 carbon atoms.

The alkyl group in the formula (A) and the formula (E) is more preferably unsubstituted.

Preferred examples of the compound include anthracene, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, and piperidine. More preferred examples of the compound include an imidazole structure, a diazabicyclo structure, a ytterbium hydroxide structure, a ruthenium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure. a compound; an alkylamine derivative having a hydroxyl group and/or an ether bond; and an aniline derivative having a hydroxyl group and/or an ether bond.

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, and benzimidazole. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, and 1,8-diazabicyclo[5,4,0]undec-7-ene. Examples of the compound having a ruthenium hydroxide structure include triarylsulfonium hydroxide, benzamidine methylhydrazine hydroxide, and barium hydroxide having a 2-sided oxyalkyl group, particularly triphenylphosphonium hydroxide or hydrogen hydroxide ( Tert-butylphenyl)anthracene, bis(t-butylphenyl)phosphonium hydroxide, benzamidine methylthiophene hydroxide, and 2-oxopropylpropylthiophene hydroxide. The compound having a ruthenium carboxylate structure is a compound in which an anion portion of a compound having a ruthenium hydroxide structure is changed to a carboxylate group, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate. Examples of the compound having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of the compound having an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of the alkylamine derivative having a hydroxyl group and/or an ether bond include ethanolamine, diethanolamine, triethanolamine, and tris(methoxyethoxyethyl)amine. Examples of the aniline derivative having a hydroxyl group and/or an ether bond include N,N-bis(hydroxyethyl)aniline.

Other preferred basic compounds include a phenoxy-containing amine compound, a phenoxy-containing ammonium salt compound, a sulfonate group-containing amine compound, and a sulfonate group-containing ammonium salt compound.

In the phenoxy-containing amine compound, the phenoxy-containing ammonium salt compound, the sulfonate group-containing amine compound, and the sulfonate group-containing ammonium salt compound, at least one alkyl group is preferably bonded to the nitrogen atom. Further, an alkyl group preferably contains an oxygen atom to form an oxyalkylene group. The number of alkyloxy groups in the molecule is 1 or more, preferably 3 to 9, more preferably 4 to 6. Among the alkylene groups, an alkyloxy group having a structure of -CH ₂ CH ₂ O-, -CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O- is preferred.

Specific examples of phenoxy-containing amine compounds, phenoxy-containing ammonium salt compounds, sulfonate-containing amine compounds, and sulfonate-containing ammonium salt compounds include, but are not limited to, US Patent Application Publication No. 2007 Compound (C1-1) to compound (C3-3) as described in paragraph [0066].

As the basic compound, a nitrogen-containing organic compound having a group capable of leaving under the action of an acid can also be used. Examples of the compound include a compound represented by the following formula (F). Incidentally, the compound represented by the following formula (F) exhibits an effective alkalinity in the system by eliminating a group capable of leaving under the action of an acid.

In the formula (F), each Ra independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Further, when n = 2, the two Ra may be the same or different, and the two Ra may be combined with each other to form a divalent heterocycloalkyl group (the number of carbon atoms is preferably 20 or less) or a derivative thereof.

Each Rb independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aromatic group. An alkyl group, which is limited to, in -C(Rb)(Rb)(Rb), when one or more Rb is a hydrogen atom, at least one of the remaining Rb is a cyclopropyl or 1-alkoxy alkane base.

At least two Rbs may be combined to form an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group or a derivative thereof.

n represents an integer of 0 to 2, m represents an integer of 1 to 3, and n + m = 3.

In the formula (F), each of the alkyl group, the cycloalkyl group, the aryl group and the aralkyl group represented by Ra and Rb may be, for example, a hydroxyl group, a cyano group, an amine group, a pyrrolidinyl group, a piperidinyl group, a morpholinyl group, and the like. Substituted by a functional group of a pendant oxy group, an alkoxy group or a halogen atom.

Specific examples of the compound represented by the formula (F) are explained below, but the invention is not limited thereto.

The compound represented by the formula (F) can be synthesized based on, for example, JP-A-2009-199021.

The molecular weight of the basic compound (D) is preferably from 250 to 2,000, more preferably from 400 to 1,000. The molecular weight of the basic compound is preferably 400 or more, more preferably 500 or more, still more preferably 600 or more, from the viewpoint of further lowering the LWR and ensuring the squareness of the pattern.

One of these basic compounds (D) may be used alone, or a combination thereof Use two or more than two.

In the present invention, the amount of the basic compound is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 5% by mass based on the solid content of the resin composition (I) or the resin composition (II).

The ratio of the acid generator to the basic compound used is preferably an acid generator/basic compound (mole ratio) = 2.5 to 300. That is, in view of sensitivity and resolution, the molar is preferably 2.5 or more; and the self-inhibiting resist pattern is lowered from the viewpoint of a decrease in resolution due to aging after exposure to heat treatment. It should be noted that the molar is preferably 300 or less. The acid generator/basic compound (mole ratio) is more preferably from 5.0 to 200, still more preferably from 7.0 to 150.

Further, the composition preferably contains a basic compound or an ammonium salt compound (hereinafter sometimes referred to as "compound (D')") which is reduced in alkalinity upon irradiation with actinic rays or radiation as a basic compound.

The compound (D') is preferably a compound (D-1) having a basic functional group or an ammonium group and capable of generating an acidic functional group upon irradiation with actinic rays or radiation. That is, the compound (D') is preferably a basic compound having a basic functional group and a group capable of generating an acidic functional group upon irradiation with actinic rays or radiation, or having an ammonium group and capable of using actinic rays Or an ammonium salt compound which generates a group of an acidic functional group upon irradiation with radiation.

The compound which is produced by decomposition of the compound (D') or the compound (D-1) upon irradiation with actinic rays or radiation and whose alkalinity is lowered includes the following formula (PA-I), formula (PA-II), and formula ( Compound represented by PA-III), and can be used in all aspects of LWR, local pattern size uniformity and DOF From the viewpoint of obtaining an excellent effect at a high level, a compound represented by the formula (PA-II) and the formula (PA-III) is preferred.

The compound represented by the formula (PA-I) is described below.

QA ₁ -(X) _n -BR (PA-I)

In the formula (PA-I), A ₁ represents a single bond or a divalent linking group.

Q represents -SO ₃ H or -CO ₂ H. Q corresponds to an acidic functional group which is generated upon irradiation with actinic rays or radiation.

X represents -SO ₂ - or -CO-.

n represents 0 or 1.

B represents a single bond, an oxygen atom or -N(Rx)-.

Rx represents a hydrogen atom or a monovalent organic group.

R represents a monovalent organic group having a basic functional group or a monovalent organic group having an ammonium group.

The divalent linking group of A ₁ is preferably a divalent linking group having a carbon number of 2 to 12, and examples thereof include an alkylene group and a stretching phenyl group. The alkyl group having at least one fluorine atom is more preferably, and its carbon number is preferably from 2 to 6, more preferably from 2 to 4. The alkyl chain may contain a linking group such as an oxygen atom and a sulfur atom. The alkylene group is preferably 30% to 100% by number of an alkylene group in which a hydrogen atom is substituted by a fluorine atom, more preferably an alkylene group having a fluorine atom bonded to a carbon atom of the Q moiety, and more preferably The perfluoroalkylene group is more preferably a perfluoroethyl, perfluoropropanyl or perfluorobutylene.

The monovalent organic group in Rx is preferably a monovalent organic group having a carbon number of 4 to 30, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group.

The alkyl group in Rx may have a substituent and is preferably a linear or branched alkyl group having a carbon number of 1 to 20, and the alkyl chain may contain an oxygen atom, a sulfur atom or a nitrogen atom.

Incidentally, the alkyl group having a substituent particularly includes a group in which a cycloalkyl group is substituted on a linear or branched alkyl group (for example, adamantylmethyl group, adamantylethyl group, cyclohexylethyl group, and camphor residue). base).

The cycloalkyl group in Rx may have a substituent and is preferably a cycloalkyl group having a carbon number of 3 to 20, and the cycloalkyl group may have an oxygen atom in the ring.

The aryl group in Rx may have a substituent and is preferably an aryl group having a carbon number of 6 to 14.

The aralkyl group in Rx may have a substituent and is preferably an aralkyl group having a carbon number of 7 to 20.

The alkenyl group in Rx may have a substituent and contain, for example, a group having a double bond at any position of the alkyl group described as Rx.

Preferred examples of the partial structure of the basic functional group include a crown ether structure, a primary amine to a tertiary amine structure, and a nitrogen-containing heterocyclic structure (e.g., pyridine, imidazole, pyrazine).

Preferred examples of the partial structure of the ammonium group include a primary to tertiary ammonium structure, a pyridinium structure, an imidazolium structure, and a pyrazinium structure.

The basic functional group is preferably a functional group having a nitrogen atom, more preferably a structure having a primary amino group to a tertiary amino group or a nitrogen-containing heterocyclic structure. In these structures, from the viewpoint of enhancing alkalinity, it is preferred that all atoms adjacent to the nitrogen atom contained in the structure are carbon atoms or hydrogen atoms. In addition, in view of enhancing alkalinity, the electron functional groups (such as carbonyl, sulfonyl, cyano and halogen atoms) are pulled. It is preferably not directly bonded to the nitrogen atom.

The monovalent organic group in the monovalent organic group (group R) having such a structure is preferably an organic group having a carbon number of 4 to 30, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. Base and alkenyl group. Each of these groups may have a substituent.

Alkyl, cycloalkyl, aryl, aralkyl and alkenyl groups of R containing a basic functional group or an ammonium group-containing alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group and an alkenyl group, and Rx The alkyl, cycloalkyl, aryl, aralkyl and alkenyl groups are the same.

Examples of the substituent which the above various groups may have include a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group (preferably having a carbon number of 3 to 10), and an aryl group (a carbon number is preferably 6). To 14), an alkoxy group (preferably having 1 to 10 carbon atoms), a mercapto group (preferably having 2 to 20 carbon atoms), a decyloxy group (preferably having 2 to 10 carbon atoms), and an alkoxycarbonyl group ( The carbon number is preferably from 2 to 20) and the amine fluorenyl group (the number of carbon atoms is preferably from 2 to 20). The cyclic structure in the aryl group, the cycloalkyl group and the like may further have an alkyl group (preferably having 1 to 20 carbon atoms) as a substituent. The amine fluorenyl group may have one or two alkyl groups (preferably having 1 to 20 carbon atoms) as a substituent.

In the case where B is -N(Rx)-, R and Rx are preferably combined to form a ring. By forming a ring structure, stability can be enhanced and the storage stability of the composition using this compound can also be enhanced. The carbon number constituting the ring is preferably from 4 to 20, and the ring may be monocyclic or polycyclic, and may contain an oxygen atom, a sulfur atom or a nitrogen atom.

Examples of monocyclic structures include a 4- to 8-membered ring containing a nitrogen atom. Multi-ring Examples of the structure include a structure composed of two single ring structures or a combination of three or more single ring structures. The monocyclic structure and the polycyclic structure may have a substituent, and preferred examples of the substituent include a halogen atom, a hydroxyl group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group (preferably having a carbon number of 3 to 10), and an aryl group (carbon). The number is preferably 6 to 14), the alkoxy group (preferably having 1 to 10 carbon atoms), the fluorenyl group (preferably having 2 to 15 carbon atoms), and the decyloxy group (preferably having 2 to 15 carbon atoms). The alkoxycarbonyl group (preferably having 2 to 15 carbon atoms) and the amine fluorenyl group (preferably having 2 to 20 carbon atoms). The cyclic structure in the aryl group, the cycloalkyl group and the like may further have an alkyl group (preferably having a carbon number of 1 to 15) as a substituent. The amine fluorenyl group may have one or two alkyl groups (preferably having 1 to 15 carbon atoms) as a substituent.

Among the compounds represented by the formula (PA-I), a compound in which the Q moiety is a sulfonic acid can be synthesized using a general sulfonium amination reaction. For example, the compound can be obtained by reacting a sulfonyl halide moiety of a bissulfonyl halide compound selectively with an amine compound to form a sulfonamide bond followed by hydrolysis of another sulfonyl halide. Part of the method; or a method of ring-opening a cyclic sulfonic anhydride by reacting with an amine compound.

The compound represented by the formula (PA-II) is described below.

Q ₁ -X ₁ -NH-X ₂ -Q ₂ (PA-II)

In the formula (PA-II), Q ₁ and Q ₂ each independently represent a monovalent organic group, and the restriction condition is that any of Q ₁ and Q ₂ has a basic functional group. Q ₁ and Q ₂ may also be combined to form a ring and the ring formed has a basic functional group.

X ₁ and X ₂ each independently represent -CO- or -SO ₂ -.

Here, -NH- corresponds to when produced by irradiation with actinic rays or radiation An acidic functional group.

The monovalent organic group as Q ₁ and Q ₂ in the formula (PA-II) is preferably a monovalent organic group having a carbon number of 1 to 40, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. Base and alkenyl group.

The alkyl group in Q ₁ and Q ₂ may have a substituent, and is preferably a linear or branched alkyl group having a carbon number of 1 to 30, and the alkyl chain may contain an oxygen atom, a sulfur atom or a nitrogen atom.

The cycloalkyl group in Q ₁ and Q ₂ may have a substituent, and is preferably a cycloalkyl group having a carbon number of 3 to 20, and the cycloalkyl group may have an oxygen atom or a nitrogen atom in the ring.

The aryl group in Q ₁ and Q ₂ may have a substituent and is preferably an aryl group having a carbon number of 6 to 14.

The aralkyl group in Q ₁ and Q ₂ may have a substituent and is preferably an aralkyl group having a carbon number of 7 to 20.

The alkenyl group in Q ₁ and Q ₂ may have a substituent and include a group having a double bond at any position of the above alkyl group.

Examples of the substituent which each of these groups may have include a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group (preferably having a carbon number of 3 to 10), and an aryl group (a carbon number is preferably 6). To 14), an alkoxy group (preferably having 1 to 10 carbon atoms), a mercapto group (preferably having 2 to 20 carbon atoms), a decyloxy group (preferably having 2 to 10 carbon atoms), and an alkoxycarbonyl group ( The carbon number is preferably from 2 to 20) and the amine fluorenyl group (the number of carbon atoms is preferably from 2 to 10). The cyclic structure in the aryl group, the cycloalkyl group and the like may further have an alkyl group (preferably having 1 to 10 carbon atoms) as a substituent. The amine fluorenyl group may have an alkyl group (the number of carbon atoms is preferably from 1 to 10) As a substituent. The alkyl group having a substituent includes, for example, a perfluoroalkyl group such as a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, and a perfluorobutyl group.

The preferred partial structure of the basic functional group contained in at least one of Q ₁ or Q ₂ is the same as that of the preferred functional group contained in R of the formula (PA-I).

a structure in which Q ₁ and Q _{2 are} combined to form a ring and the ring formed has a basic functional group, and an organic group such as Q ₁ and Q ₂ is further subjected to an alkyl group, an oxy group, an imine group or the like. The structure of the bond.

In the formula (PA-II), at least one of X ₁ and X ₂ is preferably -SO ₂ -.

The compound represented by the formula (PA-III) is described below.

Q ₁ -X ₁ -NH-X ₂ -A ₂ -(X ₃ ) _m -BQ ₃ (PA-III)

In the formula (PA-III), Q ₁ and Q ₃ each independently represent a monovalent organic group, and the restriction condition is that any of Q ₁ and Q ₃ has a basic functional group. Q ₁ and Q ₃ may also be combined to form a ring and the ring formed has a basic functional group.

X ₁ , X ₂ and X ₃ each independently represent -CO- or -SO ₂ -.

A ₂ represents a divalent linking group.

B represents a single bond, an oxygen atom or -N(Qx)-.

Qx represents a hydrogen atom or a monovalent organic group.

In the case where B is -N(Qx)-, Q ₃ and Qx may be combined to form a ring.

m represents 0 or 1.

Here, -NH- corresponds to an acidic functional group which is generated upon irradiation with actinic rays or radiation.

Q ₁ in formula (PA-II) in the Q ₁ has the same meaning.

Examples of the organic group of Q ₃ are the same as those of the organic group of Q ₁ and Q _{2 in} the formula (PA-II).

A structure in which Q ₁ and Q _{3 are} combined to form a ring and the ring formed has a basic functional group, and an organic group such as Q ₁ and Q ₃ is further bonded via an alkyl group, an oxy group, an imine group or the like. Structure.

The divalent linking group in A ₂ is preferably a divalent linking group having a carbon number of 1 to 8 and containing a fluorine atom, and examples thereof include an alkylene group having a fluorine atom having 1 to 8 carbon atoms, And a phenyl group containing a fluorine atom. The alkyl group having a fluorine atom is more preferred, and its carbon number is preferably from 2 to 6, more preferably from 2 to 4. The alkyl chain may contain a linking group such as an oxygen atom and a sulfur atom. The alkylene group is preferably 30% to 100% by number of an alkyl group in which a hydrogen atom is substituted by a fluorine atom, more preferably a perfluoroalkylene group, and even more preferably a perfluoroethylene group having a carbon number of 2 to 4. alkyl.

The monovalent organic group in Qx is preferably an organic group having 4 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. Examples of alkyl, cycloalkyl, aryl, aralkyl and alkenyl are the same as Rx in formula (PA-I).

In the formula (PA-III), each of X ₁ , X ₂ and X _{3 is} preferably -SO ₂ -.

The compound (D') is preferably an onium salt compound of a compound represented by the formula (PA-I), the formula (PA-II) or the formula (PA-III), or a formula (PA-I) or a formula (PA- Or a salt compound of the compound represented by the formula (PA-III), more preferably a compound represented by the following formula (PA1) or (PA2):

In formula (PAl) in, R _'201, R' ₂₀₂ and R _'203 independently represents an organic group, and specific examples of component (B) of formula ZI of R _201, R _202, and specific examples of R ₂₀₃ the same.

X ^- represents a sulfonate or carboxylate anion produced by eliminating a hydrogen atom in the -SO ₃ H moiety or the -COOH moiety of the compound represented by the formula (PA-I), or by eliminating the formula (PA-II) Or an anion produced by a hydrogen atom in the -NH- moiety of the compound represented by the formula (PA-III).

In formula (PA2), R _'204 and R' ₂₀₅ independently represents a specific example of the same aryl, alkyl or cycloalkyl group, and specific examples of component (B) of formula ZII of R ₂₀₄ and R ₂₀₅ is .

X ^- represents a sulfonate or carboxylate anion produced by eliminating a hydrogen atom in the -SO ₃ H moiety or the -COOH moiety of the compound represented by the formula (PA-I), or by eliminating the formula (PA-II) Or an anion produced by a hydrogen atom in the -NH- moiety of the compound represented by the formula (PA-III).

The compound (D') decomposes upon irradiation with actinic rays or radiation to give, for example, a compound represented by the formula (PA-I), the formula (PA-II) or the formula (PA-III).

The compound represented by the formula (PA-I) has a sulfonic acid group or a carboxylic acid group and a basic functional group or an ammonium group, thereby lowering the alkalinity compared with the compound (D') Or a compound that eliminates or becomes alkaline from acidic.

The compound represented by the formula (PA-II) or the formula (PA-III) has an organic sulfonylimido group or an organic carbonylimino group and a basic functional group, thereby lowering the basicity compared with the compound (D') Or a compound that eliminates or becomes alkaline from acidic.

In the present invention, the expression "lower alkalinity when irradiated with actinic rays or radiation" means the acceptor property of the proton (the acid generated when irradiated with actinic rays or radiation) of the compound (D') (acceptor property) ) is reduced by irradiation with actinic rays or radiation. The expression "reduction in receptor characteristics" means when an equilibrium reaction of a compound having a basic functional group with a proton to produce a non-covalent bond complex in the form of a proton adduct or when a counter cation of an ammonium group-containing compound is caused When the equilibrium reaction with the exchange of protons occurs, the equilibrium constant of the chemical equilibrium decreases.

In this manner, the resist film contains the compound (D') having a reduced alkalinity upon irradiation with actinic rays or radiation, so that the acceptor property of the compound (D') can be sufficiently exhibited in the unexposed region. And an unintended reaction between the acid or the like diffused from the exposed region and the resin (A) can be suppressed; and in the exposed region, the acceptor property of the compound (D') is lowered, and the acid and the resin are successfully performed. (A) The expected response. This mechanism of operation is considered to contribute to obtaining an excellent pattern of line width variation (LWR), local pattern size uniformity, focus latitude (DOF), and pattern outline.

Incidentally, the alkalinity can be determined by measuring the pH value, or a commercially available software can be used to calculate the calculated value.

Specific examples of the compound (D') capable of producing a compound represented by the formula (PA-I) upon irradiation with actinic rays or radiation are explained below, but the present invention is not limited thereto.

These compounds can be utilized by using JP-T-11-501909 (as used herein) The term "JP-T" means "the Japanese translation of the PCT patent application" or the salt exchange method described in JP-A-2003-246786, the compound represented by the formula (PA-I) or lithium thereof. A salt, a sodium salt or a potassium salt, and a hydroxide, bromide, chloride or the like of barium or strontium are easily synthesized. The synthesis can also be carried out according to the synthesis method described in JP-A-7-333851.

Specific examples of the compound (D') capable of producing a compound represented by the formula (PA-II) or the formula (PA-III) upon irradiation with actinic rays or radiation are explained below, but the present invention is not limited thereto.

These compounds can be easily synthesized by using a general sulfonation reaction or a sulfoximation reaction. For example, the compound can be obtained by selectively reacting a sulfonyl halide moiety of the bissulfonyl halide compound with a moiety represented by the formula (PA-II) or formula (PA-III). a method in which a structural amine, an alcohol or an analog thereof reacts to form a sulfonamide bond or a sulfonate bond, followed by hydrolysis of another sulfonate halide moiety; or a partial structure represented by the formula (PA-II) A method in which an amine or an alcohol opens a cyclic sulfonic anhydride. An amine or an alcohol containing a partial structure represented by formula (PA-II) or formula (PA-III) can be obtained by reacting an amine or an alcohol with an acid anhydride (for example, (R'O ₂ C) ₂ O, (R'SO ₂ ) ₂ O) or an acid chloride compound (for example, R'O ₂ CCl, R'SO ₂ Cl) (R' is, for example, methyl, n-octyl or trifluoromethyl) is synthesized under basic conditions to synthesize.

In detail, the synthesis of the compound (D') can be carried out in accordance with the synthesis examples in JP-A-2006-330098 and JP-A-2011-100105 and the like.

The molecular weight of the compound (D') is preferably from 500 to 1,000.

The content of the compound (D') used in the present invention is preferably from 0.1% by mass to 20% by mass, more preferably from 0.1% by mass to 10% by mass, based on the solid content of the composition (I) or the composition (II).

[5] (E) hydrophobic resin

The resin composition (I) or the resin composition (II) (especially the resin composition (II)) used in the present invention may contain a hydrophobic resin having at least a fluorine atom or a ruthenium atom (hereinafter sometimes referred to as "hydrophobic" Resin (E) or simply "resin (E)"), especially when the composition is applied to immersion exposure. The hydrophobic resin (E) is unevenly distributed on the surface layer of the film, and when the impregnation medium is water, the static/dynamic contact angle of the surface of the resist film with respect to water and the followability of the immersion liquid can be increased.

The hydrophobic resin (E) is preferably designed to be unevenly distributed at the interface as described above, but unlike the surfactant, it is not necessary to have a hydrophilic group in the molecule and may not contribute to uniform mixing of polarity/non- Polar substance.

The hydrophobic resin (E) typically contains a fluorine atom and/or a ruthenium atom. The fluorine atom and/or the ruthenium atom in the hydrophobic resin (E) may be contained in the resin main chain or may be contained in the side chain.

When the hydrophobic resin (E) contains a fluorine atom, the resin preferably contains a fluorine atom-containing alkyl group, a fluorine atom-containing cycloalkyl group or a fluorine atom-containing aryl group as a partial structure of a fluorine atom.

The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms and more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and may further have a fluorine atom. Substituents other than the substituents.

The cycloalkyl group of a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.

The aryl group of the fluorine atom is an aryl group (such as a phenyl group or a naphthyl group) in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than the fluorine atom.

The preferred fluorine atom-containing alkyl group, fluorine atom-containing cycloalkyl group, and fluorine atom-containing aryl group include a group represented by the following formula (F2) to formula (F4), but the invention is not limited thereto.

In the formulae (F2) to (F4), R ₅₇ to R ₆₈ each independently represent a hydrogen atom, a fluorine atom or an alkyl group (straight or branched chain), and the restriction condition is at least one of R ₅₇ to R ₆₁ And at least one of R ₆₂ to R ₆₄ and at least one of R ₆₅ to R ₆₈ each independently represent a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom (the number of carbon atoms is preferably from 1 to 4) ).

All of R ₅₇ to R ₆₁ and R ₆₅ to R _{67 are} preferably fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are each preferably an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom (the number of carbon atoms is preferably from 1 to 4), more preferably a perfluoroalkyl group having a carbon number of from 1 to 4. R ₆₂ and R ₆₃ may be combined with each other to form a ring.

Specific examples of the group represented by the formula (F2) include p-fluorophenyl group, pentafluorophenyl group, and 3,5-bis(trifluoromethyl)phenyl group.

Specific examples of the group represented by the formula (F3) include trifluoromethyl, pentafluoropropyl, pentafluoroethyl, heptafluorobutyl, hexafluoroisopropyl, heptafluoroisopropyl, hexafluoro (2- Methyl)isopropyl, nonafluorobutyl, octafluoroisobutyl, nonafluorohexyl, nonafluorobutanyl, perfluoroisopentyl, perfluorooctyl, perfluoro(trimethyl)hexyl, 2 , 2,3,3-tetrafluorocyclobutyl and perfluorocyclohexyl. Hexafluoroisopropyl, heptafluoroisopropyl, hexafluoro(2-methyl)isopropyl, octafluoroisobutyl, nonafluoro-t-butyl and perfluoroisopentyl are preferred, and hexafluoroisopropyl The base and heptafluoroisopropyl are preferred.

Specific examples of the group represented by the formula (F4) include -C(CF ₃ ) ₂ OH, -C(C ₂ F ₅ ) ₂ OH, -C(CF ₃ )(CH ₃ )OH, and -CH(CF _{3 )} OH, wherein -C(CF ₃ ) ₂ OH is preferred.

The partial structure of the fluorine-containing atom may be directly bonded to the main chain, or may be via an alkyl group, a phenyl group, an ether bond, a thioether bond, a carbonyl group, an ester bond, a guanamine bond, or an amine. A group selected from a group consisting of a urethane bond and a ureido bond or a group formed by combining two or more of these groups and a bond is bonded to the main chain.

Suitable repeating units having a fluorine atom include the following.

In the formula, R ₁₀ and R ₁₁ each independently represent a hydrogen atom, a fluorine atom or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having a carbon number of 1 to 4 and may have a substituent, and the alkyl group having a substituent particularly includes a fluorinated alkyl group.

W ₃ to W ₆ each independently represent an organic group having at least one or more than one fluorine atom, and the group particularly includes atomic groups of (F2) to (F4).

In addition to these, the hydrophobic resin (E) may contain a unit shown below as a repeating unit having a fluorine atom.

In the formula, R ₄ to R ₇ each independently represent a hydrogen atom, a fluorine atom or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having a carbon number of 1 to 4 and may have a substituent, and the alkyl group having a substituent particularly includes a fluorinated alkyl group.

However, at least one of R ₄ to R ₇ represents a fluorine atom. R ₄ and R ₅ or R ₆ and R ₇ may form a ring.

W ₂ represents an organic group having at least one fluorine atom, and the group particularly includes atomic groups of (F2) to (F4).

L ₂ represents a single bond or a divalent linking group. The divalent linking group is a substituted or unsubstituted extended aryl group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkyl group, -O-, -SO ₂ -, -CO-, -N(R)- (wherein R represents a hydrogen atom or an alkyl group), -NHSO ₂ -, or a divalent linking group formed by combining a plurality of these groups.

Q represents an alicyclic structure. The alicyclic structure may have a substituent and may be a monocyclic or polycyclic ring, and in the case of a polycyclic structure, the structure may be a crosslinked structure. The monocyclic structure is preferably a cycloalkyl group having a carbon number of 3 to 8, and examples thereof include a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. Examples of the polycyclic structure include a group having a bicyclic, tricyclic or tetracyclic structure and having a carbon number of 5 or more. The cycloalkyl group having 6 to 20 carbon atoms is preferred, and examples thereof include adamantyl group, norbornyl group, dicyclopentyl group, tricyclodecyl group, and tetracyclododecyl group. A portion of the carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom. In summary, Q is preferably, for example, norbornyl, tricyclodecyl or tetracyclododecyl.

Specific examples of repeating units having a fluorine atom are described below, but the present invention Ming is not limited to this.

In a particular example, X ₁ represents a hydrogen atom, -CH ₃ , -F or -CF ₃ . X ₂ represents -F or -CF ₃ .

The hydrophobic resin (E) may contain a ruthenium atom. The resin preferably has an alkyl fluorenyl structure (preferably a trialkyl decyl group) or a cyclic siloxane structure as a partial structure containing a ruthenium atom.

Specific examples of the alkyl fluorenyl structure and the cyclic oxane structure include a group represented by the following formula (CS-1) to formula (CS-3):

In the formulae (CS-1) to (CS-3), R ₁₂ to R ₂₆ each independently represent a straight-chain or branched alkyl group (preferably having 1 to 20 carbon atoms) or a cycloalkyl group (compared to carbon number) Good for 3 to 20).

L ₃ to L ₅ each represents a single bond or a divalent linking group. a divalent linking group is the only member selected from the group consisting of an alkyl group, a phenyl group, an ether bond, a thioether bond, a carbonyl group, an ester bond, a guanamine bond, a urethane bond, and a urea bond. A combination of two or more members (the total carbon number is preferably 12 or less).

n represents an integer from 1 to 5. n is preferably an integer of 2 to 4.

Specific examples of the repeating unit having a group represented by the formula (CS-1) to the formula (CS-3) are explained below, but the invention is not limited thereto. In a particular example, X ₁ represents a hydrogen atom, -CH ₃ , -F or -CF ₃ .

Further, the hydrophobic resin (E) may contain at least one group selected from the group consisting of (x) to (z): (x) acid group; (y) a group having a lactone structure, an acid anhydride group a group of acid imide groups; and (z) a group capable of decomposing under the action of an acid.

Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, Sulfonic acid group, sulfonylamino group, sulfonimide group, (alkylsulfonyl)(alkylcarbonyl)methylene group, (alkylsulfonyl)(alkylcarbonyl)imide group, bis(alkane) Methylcarbonyl, methylene, bis(alkylcarbonyl)imido, bis(alkylsulfonyl)methylene, bis(alkylsulfonyl)imide, tris(alkylcarbonyl)methylene And a tris(alkylsulfonyl)methylene group.

Preferred acid groups are fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis(alkylcarbonyl)methylene groups.

The repeating unit having an (x) acid group includes, for example, a repeating unit in which an acid group is directly bonded to a resin main chain, such as a repeating unit formed of acrylic acid or methacrylic acid; and an acid group bonded to the resin main chain via a linking group Further, an acid group may be introduced into a repeating unit in the terminal of the polymer chain by polymerization using an acid group-containing polymerization initiator or a chain transfer agent. All of these situations are better. The repeating unit having an (x) acid group may have at least a fluorine atom or a germanium atom.

The content of the repeating unit having a (x) acid group is preferably from 1 mol% to 50 mol%, more preferably from 3 mol% to 35 mol%, based on all the repeating units in the hydrophobic resin (E). More preferably from 5 mol% to 20 mol%.

Specific examples of the repeating unit having the (x) acid group are explained below, but the present invention is not limited thereto. In the formula, Rx represents a hydrogen atom, CH ₃ , CF ₃ or CH ₂ OH.

(y) The group containing a lactone structure, an acid anhydride group or an acid imine group is preferably a group having a lactone structure.

The repeating unit containing such a group is, for example, a repeating unit in which the group is directly bonded to a resin main chain, such as a repeating unit formed of an acrylate or a methacrylate. This repeating unit may be a repeating unit in which the group is bonded to the resin main chain via a linking group. Alternatively, in this repeating unit, the group may be introduced into the resin end by polymerization using a polymerization initiator or a chain transfer agent containing the group.

Examples of the repeating unit having a group having a lactone structure are the same as the examples of the repeating unit having a lactone structure described above in the paragraph of the resin (A).

The content of the repeating unit having a lactone-containing group, an acid anhydride group or an acid imine group is preferably from 1 mol% to 100 mol%, more preferably 3 mol%, based on all the repeating units in the hydrophobic resin. Ears are up to 98% by mole, and even more preferably from 5 moles to 95% by mole.

Examples of the repeating unit having a group (z) capable of decomposing under the action of an acid contained in the hydrophobic resin (E) are the same as those of the repeating unit having an acid-decomposable group described in the resin (A). The repeating unit having (z) a group capable of decomposing under the action of an acid may contain at least a fluorine atom or a halogen atom. In the hydrophobic resin (E), the content of the repeating unit having (z) a group capable of decomposing under the action of an acid is preferably from 1 mol% to 80 mol% based on all the repeating units in the resin (E). More preferably, it is 10 mol% to 80 mol%, still more preferably 20 mol% to 60 mol%.

The hydrophobic resin (E) may further contain a repeating unit represented by the following formula (III):

In the formula (III), R _c31 represents a hydrogen atom, an alkyl group (which may be substituted by a fluorine atom or the like), a cyano group or a -CH ₂ -O- _ac2 group, wherein R _ac2 represents a hydrogen atom, an alkyl group. Or 醯基. R _{c31 is} preferably a hydrogen atom, a methyl group, a methylol group or a trifluoromethyl group, more preferably a hydrogen atom or a methyl group.

R _c32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group or an aryl group. These groups may be substituted with a group of a fluorine atom or a halogen atom.

L _c3 represents a single bond or a divalent linking group.

In the formula (III), the alkyl group of R _c32 is preferably a linear or branched alkyl group having a carbon number of 3 to 20.

The cycloalkyl group is preferably a cycloalkyl group having a carbon number of 3 to 20.

The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.

The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group, and these groups may have a substituent.

R _{c32 is} preferably an unsubstituted alkyl group or an alkyl group substituted by a fluorine atom.

The divalent linking group of L _c3 is preferably an alkylene group (preferably having 1 to 5 carbon atoms), an ether bond, a phenyl group or an ester bond (group represented by -COO-).

The content of the repeating unit represented by the formula (III) is preferably from 1 mol% to 100 mol%, more preferably from 10 mol% to 90 mol%, more preferably from 10 mol% to 90 mol%, based on all the repeating units in the hydrophobic resin. 30% to 70% by mole.

It is also preferred that the hydrophobic resin (E) further contains a repeating unit represented by the following formula (CII-AB):

In the formula (CII-AB), R _c11 ' and R _c12 ' each independently represent a hydrogen atom, a cyano group, a halogen atom or an alkyl group.

Z _c ' represents an atomic group for forming an alicyclic structure containing two carbon atoms (CC) bonded to Z _c '.

The content of the repeating unit represented by the formula (CII-AB) is preferably from 1 mol% to 100 mol%, more preferably from 10 mol% to 90 mol%, based on all the repeating units in the hydrophobic resin, more preferably Good is 30% to 70% by mole.

Specific examples of the repeating unit represented by the formula (III) and the formula (CII-AB) are explained below, but the invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN.

In the case where the hydrophobic resin (E) contains a fluorine atom, the fluorine atom content is preferably from 5% by mass to 80% by mass, and more preferably from 10% by mass to 80% by mass, based on the weight average molecular weight of the hydrophobic resin (E). Further, the repeating unit of the fluorine-containing atom is preferably from 10 mol% to 100 mol%, more preferably from 30 mol% to 100 mol%, based on all the repeating units contained in the hydrophobic resin (E).

In the case where the hydrophobic resin (E) contains a ruthenium atom, the ruthenium atom content is preferably from 2% by mass to 50% by mass, and more preferably from 2% by mass to 30% by mass, based on the weight average molecular weight of the hydrophobic resin (E). Further, the repeating unit containing a halogen atom preferably accounts for 10 mol% to 100 mol%, more preferably 20 mol% to 100 mol%, based on all the repeating units contained in the hydrophobic resin (E).

The weight average molecular weight of the hydrophobic resin (E) is preferably from 1,000 to 100,000, more preferably from 1,000 to 50,000, still more preferably from 2,000 to 15,000, based on the standard polystyrene.

For the hydrophobic resin (E), one type or a plurality of types of hydrophobic resins (E) may be used in combination.

In the case where the resin composition (I) or the resin composition (II) contains (E) a hydrophobic resin, the content of the hydrophobic resin (E) in each composition is preferably in terms of the total solid content in the composition of the present invention. From 0.01% by mass to 20% by mass, more preferably from 0.05% by mass to 10% by mass, still more preferably from 0.1% by mass to 8% by mass, still more preferably from 0.1% by mass to 5% by mass.

In the hydrophobic resin (E), similarly to the resin (A), the content of impurities such as metal is preferably small, but the content of the residual monomer or oligomer component is preferably from 0.01% by mass to 5. The mass% is more preferably from 0.01% by mass to 3% by mass, still more preferably from 0.05% by mass to 1% by mass. Due to the content within this range, a resin composition which does not contain a liquid foreign substance and whose sensitivity and its like characteristics do not change with aging can be obtained. Further, in view of resolution, resist profile, resist pattern sidewall, roughness, and the like, the molecular weight distribution (Mw/Mn, sometimes referred to as "polydispersity") is preferably from 1 to 5, more preferably It is 1 to 3, more preferably 1 to 2.

As the hydrophobic resin (E), various commercially available products can be used, or a synthetic resin can be obtained by a conventional method (for example, radical polymerization). Examples of general synthetic methods include: a batch polymerization method in which a monomer substance and an initiator are dissolved in a solvent and a solution is heated to effect polymerization; and a dropwise addition polymerization method in which heating is performed for 1 hour to 10 hours A solution containing a monomer substance and an initiator is added dropwise to the solvent. The dropwise addition polymerization method is preferred.

The reaction solvent, the polymerization initiator, the reaction conditions (for example, temperature, concentration), and the purification method after the reaction are the same as those described for the resin (A), but in the synthesis of the hydrophobic resin (E), the concentration at the time of the reaction is preferably 30% by mass to 50% by mass.

Specific examples of the hydrophobic resin (E) are explained below. Further, the repeating unit molar ratio (corresponding to the repeating unit from the left) of each resin, the weight average molecular weight, and the polydispersity are shown later in the table.

[6] (F) surfactant

The resin composition (I) or the resin composition (II) used in the present invention may or may not contain a surfactant, but in the case of containing a surfactant, it preferably contains a fluorine-containing surfactant and/or Any one or two or more of a cerium-containing surfactant (a fluorosurfactant, a cerium-containing surfactant, and a surfactant containing a fluorine atom and a ruthenium atom).

The resin composition (I) or the resin composition (II) used in the present invention can be provided at a use wavelength of 250 nm or less, particularly 220 nm or less, by containing a surfactant. The resist pattern is improved in sensitivity, resolution, and adhesion when the light source is exposed, and the development defect is reduced.

Examples of fluorosurfactants and/or cerium-containing surfactants include beauty The surfactants described in paragraph [2008] of the Japanese Patent Application Publication No. 2008/0248425, such as EFtop EF301 and EF303 (produced by Shin-Akita Kasei KK); Florad FC430, 431 and 4430 (produced by Sumitomo 3M Inc.); Megaface F171, F173, F176, F189, F113, F110, F177, F120 and R08 (by Produced by Dainippon Ink Chemical Company (DIC Corporation); containing Furlon S-382, SC101, 102, 103, 104, 105 and 106 and KH-20 (by Asahi Glass Co., Ltd.) .) Production); Troysol S-366 (manufactured by Troy Chemical); GF-300 and GF-150 (produced by Toagosei Chemical Industry Co., Ltd.) ); Furlong S-393 (produced by Seimi Chemical Co., Ltd.); Yvtos EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 and EF601 (produced by JEMCO Inc.); PF636, PF656, PF6320 and PF6520 (by Onova) Division (OMNOVA) Ltd.); and FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D and 222D (the Ni Ousi Limited (NEOS Co., Ltd.) Ltd.). Further, a polyoxyalkylene polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as the cerium-containing surfactant.

In addition to these known surfactants, surfactants can be used which employ fluoroaliphatic groups derived from fluoroaliphatic compounds and which A polymer produced by a telomerization process (also known as a short chain polymer process) or an oligomerization process (also known as an oligomer process). The fluorine-containing aliphatic compound can be synthesized by the method described in JP-A-2002-90991.

Examples of the surfactant belonging to the above surfactant include Meg Vanes F178, F-470, F-473, F-475, F-476, and F-472 (manufactured by DIC Corporation) a copolymer of a C ₆ F ₁₃ group-containing acrylate (or methacrylate) and (poly(oxyalkylene)) acrylate (or methacrylate); and a C ₃ F ₇ group-containing group Copolymer of acrylate (or methacrylate) with (poly(oxyethylidene)) acrylate (or methacrylate) and (poly(oxypropyl)) acrylate (or methacrylate) .

In the present invention, a surfactant other than the fluorine-containing surfactant and/or the barium-containing surfactant described in the paragraph [0280] of the U.S. Patent Application Publication No. 2008/0248425 may be used.

One of these surfactants may be used alone, or some of the surfactants may be used in combination.

The resin composition (I) or the resin composition (II) used in the present invention may or may not contain a surfactant, but in the case where the resin composition (I) or the resin composition (II) contains a surfactant The amount of the surfactant to be used is preferably 0.0001% by mass to 2% by mass, more preferably 0.0005% by mass to 1% by mass based on the total amount of the resin composition (I) or the resin composition (II) (excluding the solvent). .

[7] (G) Other additives

The resin composition (I) or the resin composition (II) used in the present invention may It may or may not contain barium carboxylate. Examples of the carboxylic acid hydrazine include bismuth carboxylate described in paragraphs [0605] to [0606] of U.S. Patent Application Publication No. 2008/0187860.

The ruthenium carboxylate can be synthesized by reacting ruthenium hydroxide, ruthenium hydroxide or ammonium hydroxide and a carboxylic acid with silver oxide in a suitable solvent.

In the case where the resin composition (I) or the resin composition (II) contains cerium carboxylate, the content thereof is generally 0.1% by mass to 20% by mass based on the total solid content of the composition (I) or the composition (II). It is preferably from 0.5% by mass to 10% by mass, more preferably from 1% by mass to 7% by mass.

The resin composition (I) or the resin composition (II) used in the present invention may further contain, for example, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, and for accelerating development. A compound dissolved in the agent (for example, a phenol compound having a molecular weight of 1,000 or less, or an alicyclic or aliphatic compound having a carboxyl group).

A phenolic compound having a molecular weight of 1,000 or less can be easily synthesized by a method described in, for example, JP-A-4-122938, JP-A-2-28531, U.S. Patent No. 4,916,210 or European Patent No. 219,294.

Specific examples of the alicyclic or aliphatic compound containing a carboxyl group include, but are not limited to, a carboxylic acid derivative having a steroid structure such as cholic acid, deoxycholic acid, and lithocholic acid; an adamantanecarboxylic acid derivative, adamantane Dicarboxylic acid, cyclohexanecarboxylic acid, and cyclohexanedicarboxylic acid.

The solid content of each of the resin composition (I) and the resin composition (II) used in the present invention is usually from 1.0% by mass to 15% by mass, It is preferably from 1.5% by mass to 13% by mass, more preferably from 2.0% by mass to 12% by mass. By setting the solid content concentration within the above range, the resist solution can be uniformly applied onto the substrate, and further, a resist pattern having high resolution and a rectangular outline and excellent in etching resistance can be formed. Although the cause is not clearly known, it is considered that the concentration of the solid content is 10% by mass or less, preferably 5.7% by mass or less than 5.7% by mass, and the substance in the resist solution can be suppressed (especially The photoacid generator is agglomerated so that a uniform resist film can be formed.

The solid content concentration is a weight percentage of the weight of the resist component not containing the solvent based on the total weight of the resin composition.

The resin composition (I) and the resin composition (II) used in the present invention are each filtered and filtered through a filter by dissolving the above components in a predetermined organic solvent (preferably the above mixed solvent). It is used on a predetermined support (substrate). The filter for filtration is preferably a filter made of polytetrafluoroethylene, polyethylene or nylon having a pore diameter of 0.1 μm or less, more preferably 0.05 μm or less, and then 0.05 μm or less. More preferably, it is 0.03 micrometers or less than 0.03 micrometers. When filtering through a filter, it is possible to carry out circulation filtration as described in, for example, JP-A-2002-62667, or to filter by connecting a plurality of filters in series or in parallel. In addition, the composition can be filtered multiple times. Further, a degassing treatment or the like may be applied to the composition before and after filtration through the filter.

[8] Pattern forming method

The pattern forming method of the present invention (negative pattern forming method) includes: (i) forming a first on a substrate by using the first resin composition (I) a step of a film (first resist film); (ii) forming a second film on the first film by using a second resin composition (II) different from the resin composition (I) (second resist) a step of exposing the multilayer film having the first film and the second film; and (iv) exposing the first film in the exposed multilayer film by using a developer containing an organic solvent The step of developing the film to form a negative pattern.

In the pattern forming method of the present invention, the thickness of each of the first film and the second film is preferably from 20 nm to 250 nm, more preferably from 30 nm to 250 nm, from the viewpoint of increasing the resolution. Further preferably, it is from 30 nm to 200 nm. Such a film thickness can be obtained by setting the solid content concentration in each composition within an appropriate range to impart appropriate viscosity and to enhance coatability and film formation properties.

In the pattern forming method of the present invention, the exposure step (iii) can be carried out a plurality of times.

The exposure in step (iii) can be an immersion exposure.

In the pattern forming method of the present invention, the step of forming a film on the substrate by using each of the resin composition (I) and the resin composition (II), the step of exposing the multilayer film, and the developing step can be generally known by The way to proceed.

In the pattern forming method of the present invention, the heating step can be performed a plurality of times.

In the present invention, it is preferred to further carry out at least before the exposure step (iii) or after the exposure step (iii) but before the development step (iv) Heating step.

More preferably, a pre-baking step (PB) is carried out after the film forming step (i) of the first film but before the film forming step (ii) of the second film.

It is also preferred to include a prebaking step (PB) which is carried out after the film formation of the second film but before the exposure step (iii).

Further, a post-exposure baking step (PEB) containing after the exposure step (iii) but before the development step (iv) is also preferred.

For the heating temperature, both PB and PEB are preferably carried out at 70 ° C to 150 ° C, more preferably at 80 ° C to 140 ° C.

The heating time is preferably from 30 seconds to 300 seconds, more preferably from 30 seconds to 180 seconds, still more preferably from 30 seconds to 90 seconds.

Heating may be performed using a device connected to a general exposure/developer, or may be performed using a hot plate or the like.

Due to baking, the reaction in the exposed area is accelerated, and the sensitivity and pattern profile are improved.

The wavelength of the light source used in the exposure apparatus of the present invention is not limited, and includes, for example, near-infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-ray, and electron beam, but preferably has a wavelength of 250 nm or It is less than 250 nm, more preferably 220 nm or less than 220 nm, and even more preferably from 1 nm to 200 nm. Specific examples thereof include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV (13 nm), and electron beam. . Among them, KrF excimer laser, ArF excimer laser, EUV and electron beam are preferred, and KrF excimer laser and ArF excimer laser are better.

In the present invention, the substrate on which the film is formed is not particularly limited, and an inorganic substrate such as germanium, SiN, SiO ₂ and SiN; a coated inorganic substrate such as SOG; or generally used for manufacturing a semiconductor such as an IC may be used. Or a process for fabricating a liquid crystal cell or circuit board (such as a thermal head) or a substrate for lithography of other photoprocessing processes. An organic anti-reflection film may be formed between the film and the substrate as necessary.

For example, in micromachining such as ion implantation applications, the pattern forming method of the present invention can use a stepped substrate as a substrate.

The stepped substrate is a substrate on which at least one stepped shape is formed on the substrate.

As described above, in the micromachining such as the use of a stepped substrate, a negative pattern forming method developed using an organic solvent is very suitable, but on the other hand, the pattern easily has an overcut profile. However, according to the pattern forming method, the pattern can be prevented from having an overcut profile, and a rectangular pattern is obtained.

The thickness of the multilayer film formed on the stepped substrate means the height from the bottom on the stepped substrate to the top of the formed multilayer film.

The height from the bottom of the stepped substrate to the top of the stepped shape is preferably less than the thickness of the multilayer film, and is, for example, less than 200 nm.

For example, in the case of micromachining such as ion implantation applications, a substrate obtained by patterning fins or gates on a flat substrate can be used as a stepped substrate. The thickness of the multilayer film formed by applying the resin composition (I) and the resin composition (II) to such a stepped substrate on which the fins or gates have been patterned is not intended to be self-ribbed or gated. The height to the top of the formed multilayer film, as described above, means the height from the bottom on the stepped substrate to the top of the formed multilayer film.

For ribs and gate dimensions (eg width, length, height), spacing, structure, configuration and the like, for example, the Journal of IEICE , Vol. 91, No. Phase 1, "Saisentan FinFET Process/Shuseki-ka Gijutsu; Advanced FinFET Process/Integration Technology" on pages 25-29 (2008) and Japanese Journal of Applied Physics (Jpn.J.Appl.Phys) .) , vol. 42 (2003), pp. 4142-4146, part 1, vol. 6B, June 2003 "ribbed double gates manufactured by position-dependent etching and electron beam lithography Fin-type Double-Gate Metal-Oxide-Semiconductor Field-Effect Transistors Fabricated by Orientation-Dependent Etching and Electron Beam Lithography.

In the pattern forming method of the present invention, a polar solvent such as a ketone solvent can be used for the developer in the step of developing by using an organic solvent-containing developer (hereinafter sometimes referred to as "organic developer"). , an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent, or a hydrocarbon solvent.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetonyl acetone, acetonyl acetone , ionone (ionone), diacetone alcohol (diacetonyl Alcohol), acetyl carbinol, acetophenone, methylnaphthyl ketone, isophorone, and propyl carbonate.

Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate. Ester, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate , 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate and propyl lactate.

Examples of the alcohol solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, third butanol, isobutanol, n-hexanol, n-heptanol, n-octanol, and a sterol; a glycol-based solvent such as ethylene glycol, diethylene glycol, and triethylene glycol; and a glycol ether-based solvent such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol single Ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethylbutanol.

In addition to the above glycol ether-based solvent, examples of the ether solvent include dioxane and tetrahydrofuran.

Examples of the guanamine-based solvent that can be used include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphonium triamine (hexamethylphosphoric triamide) and 1,3-dimethyl-2-imidazolidinone.

Examples of the hydrocarbon solvent include aromatic hydrocarbon-based solvents such as toluene and xylene; and aliphatic hydrocarbon-based solvents such as pentane, hexane, and octane Alkanes and decanes.

A plurality of these solvents may be mixed, or the solvent may be used by mixing with a solvent other than the above or mixing with water. However, in order to fully exert the effects of the present invention, the water content of the entire developer is preferably less than 10% by mass, and more preferably substantially no water.

That is, the amount of the organic solvent used in the organic developer is preferably from 90% by mass to 100% by mass, and more preferably from 95% by mass to 100% by mass based on the total amount of the developer.

More specifically, the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent.

The vapor pressure of the organic developer at 20 ° C is preferably 5 kPa or less, more preferably 3 kPa or less, more preferably 2 kPa or less. By setting the vapor pressure of the organic developer to 5 kPa or less, it is possible to suppress evaporation of the developer on the substrate or in the developing cup, and to improve the temperature uniformity in the plane of the wafer, thereby improving the wafer plane. Dimensional uniformity within.

Specific examples of the solvent having a vapor pressure of 5 kPa or less include ketone solvents such as 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl pentyl) Ketone), 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, and methyl isobutyl ketone; ester solvents such as butyl acetate, Pentyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, two Ethylene glycol monoethyl ether Acid ester, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate Esters and propyl lactate; alcohol solvents such as n-propanol, isopropanol, n-butanol, second butanol, tert-butanol, isobutanol, n-hexanol, n-heptanol, n-octanol and ruthenium Alcohol; glycol-based solvents such as ethylene glycol, diethylene glycol, and triethylene glycol; glycol ether-based solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol Monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethylbutanol; an ether solvent such as tetrahydrofuran; a guanamine solvent such as N-methyl-2-pyrrolidone; N,N-dimethylacetamide and N,N-dimethylformamide; solvents based on aromatic hydrocarbons such as toluene and xylene; and solvents based on aliphatic hydrocarbons such as octane and decane.

Specific examples of the solvent having a vapor pressure of 2 kPa or less (this is a particularly preferred range) include a ketone solvent such as 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, and phenylacetone; ester solvents such as butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate , ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, and propyl lactate; alcohol solvents such as n-butanol, second butanol, third butanol, isobutanol, and hexanol Alcohol, n-heptanol, n-octanol and n-nonanol; diol-based solvents such as ethylene glycol, diethylene glycol and triethylene glycol; glycol ether based solvents such as ethylene glycol monomethyl ether, Propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethyl Glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethylbutanol; guanamine solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N N-dimethylformamide; a solvent based on an aromatic hydrocarbon such as xylene; and a solvent based on an aliphatic hydrocarbon such as octane and decane.

An appropriate amount of a surfactant may be added to the organic developer as necessary.

The surfactant is not particularly limited, but for example, an ionic or nonionic fluorine-containing surfactant and/or a cerium-containing surfactant can be used. Examples of the fluorine-containing surfactant and/or the cerium-containing surfactant include JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, and U.S. Patents 5,405,720, 5,360,692, 5,529,881, 5,296,330, Surfactants as described in 5,436,098, 5,576,143, 5,294,511 and 5,824,451. Nonionic surfactants are preferred. The nonionic surfactant is not particularly limited, but a fluorine-containing surfactant or a cerium-containing surfactant is more preferably used.

The amount of the surfactant to be used is usually 0.001% by mass to 5% by mass, preferably 0.005% by mass to 2% by mass, more preferably 0.01% by mass to 0.5% by mass, based on the total amount of the developer.

Regarding the developing method, for example, a method of immersing the substrate in a bath filled with a developer for a fixed period of time (dipping method); lifting the developer by surface tension on the surface of the substrate and maintaining the state for a fixed period of time can be applied, thereby a method of developing (puddle method); a method of spraying a developer on a surface of a substrate (spraying method); and continuously ejecting the developer on a substrate rotating at a constant speed while scanning the developer at a constant rate Method of ejecting nozzle (dynamic dispense method).

In the case where the above various developing methods include the step of ejecting the developer from the developing nozzle of the developing device to the resist film, the ejection pressure of the ejected developer (the flow rate of the developer per unit area) is preferably 2 ml / Seconds/mm 2 or less than 2 ml/sec/mm 2 , more preferably 1.5 ml/sec/mm 2 or less than 1.5 ml/sec/mm 2 , even more preferably 1 ml/sec/mm 2 or less than 1 ml/ Seconds / square millimeters. There is no specific lower limit for the flow rate, but in view of the treatment amount, it is preferably 0.2 ml/sec/mm 2 or more than 0.2 ml/sec/mm 2 .

By setting the ejection pressure of the ejected developer within the above range, pattern defects caused by resist scum after development can be greatly reduced.

Although the details of this mechanism are not clear, it is considered that since the ejection pressure is within the above range, the pressure applied to the resist film by the developer becomes small, and the resist film or the resist pattern is prevented from being inadvertently present. Fragmentation or rupture.

Here, the ejection pressure of the developer (ml/sec/mm 2 ) is the value at the exit of the developing nozzle in the developing device.

Examples of the method of adjusting the developer ejection pressure include a method of adjusting the ejection pressure with a pump or the like, and a method of supplying the developer from the pressurized canister and adjusting the pressure to change the ejection pressure.

After the step of developing using a developer containing an organic solvent, the step of terminating development by replacing the solvent with another solvent may be carried out.

Preferably, the step of developing by using a developer containing an organic solvent The step of rinsing the membrane with the rinsing solution is provided after the step.

The rinsing solution used in the rinsing step performed after the step of developing by using the developer containing the organic solvent is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used. For the rinsing solution, it is preferred to use a rinsing solution containing at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent.

Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the guanamine solvent, and the ether solvent are the same as those described above for the organic solvent-containing developer.

After the step of developing using a developer containing an organic solvent, it is more preferred to use an organic solvent selected from the group consisting of at least one solvent consisting of a ketone solvent, an ester solvent, an alcohol solvent, and a guanamine solvent. a step of rinsing the film with the rinsing solution; and more preferably a step of rinsing the film by using a rinsing solution containing an alcohol solvent or an ester solvent; and further preferably a step of rinsing the film by using a rinsing solution containing a monohydric alcohol; And the step of rinsing the film by using a rinsing solution containing a carbon number of 5 or more.

The monohydric alcohol used in the rinsing step contains a linear, branched or cyclic monohydric alcohol, and specific examples of the monohydric alcohol which can be used include 1-butanol, 2-butanol, 3-methyl-1-butanol, Tributanol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2- Heptyl alcohol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol and 4-octanol. For particularly preferred monohydric alcohols having a carbon number of 5 or greater, 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and the like.

A plurality of these components may be mixed, or the solvent may be used by mixing with an organic solvent other than the above solvent.

The water content of the rinsing solution is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less. Good development characteristics can be obtained by setting the water content to 10% by mass or less.

After the step of developing by using a developer containing an organic solvent, the vapor pressure of the rinse solution used at 20 ° C is preferably from 0.05 kPa to 5 kPa, more preferably from 0.1 kPa to 5 kPa. And the best is 0.12 kPa to 3 kPa. By setting the vapor pressure of the rinsing solution in the range of 0.05 kPa to 5 kPa, the temperature uniformity in the plane of the wafer can be improved, and in addition, the expansion due to the penetration of the rinsing solution can be suppressed, thereby improving the wafer. Dimensional uniformity in the plane.

The rinsing solution can also be used after adding an appropriate amount of a surfactant thereto.

In the rinsing step, the above-described organic solvent-containing rinsing solution is used to rinse the wafer after development using the organic solvent-containing developer. The method for the rinsing treatment is not particularly limited, but examples of the applicable method include a method of continuously spraying a rinsing solution on a substrate rotating at a constant speed (spin coating method), immersing the substrate in a bath filled with a rinsing solution A method of maintaining a fixed time (dipping method) and a method of spraying a rinsing solution on the surface of the substrate (spraying method). In summary, the rinsing treatment is preferably performed by a spin coating method, and after rinsing, the rinsing solution is removed from the substrate surface by rotating the substrate at a rotation speed of 2,000 rpm to 4,000 rpm. After the rinsing step It is also preferred to include a heating step (post-baking). The developer remaining between the patterns and inside the pattern and the rinsing solution are removed by baking. The heating step after the rinsing step is usually carried out at 40 ° C to 160 ° C, preferably at 70 ° C to 95 ° C, usually for 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

In the case where the pattern forming method of the present invention further includes a step of developing a film by using an alkali developer, examples of the alkali developer which can be used include an alkaline aqueous solution of the following: an inorganic base such as sodium hydroxide or hydrogen. Potassium oxide, sodium carbonate, sodium citrate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and Methyldiethylamine; alkanolamines such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; or cyclic amines such as pyrrole and piperidine.

The above alkaline aqueous solution may also be used after adding an alcohol and a surfactant (each appropriate amount) thereto.

The alkali concentration of the alkali developer is usually from 0.1% by mass to 20% by mass.

The pH of the alkaline developer is usually from 10.0 to 15.0.

In particular, a 2.38 mass% aqueous solution of tetramethylammonium hydroxide is preferred.

As the rinsing solution in the rinsing treatment after the alkali development, pure water is used, and pure water may be used after adding an appropriate amount of the surfactant thereto.

After the development treatment or the rinsing treatment, the treatment of removing the developer or the rinsing solution adhered to the pattern by the supercritical fluid may be performed.

The present invention also relates to an electronic component manufacturing method including the pattern forming method of the present invention and an electronic component manufactured by the manufacturing method.

The electronic component of the invention should preferably be installed in an electrical and electronic device (such as a household Electronic components, OA media related components, optical components, and communication components).

[Example]

The invention is described in more detail below with reference to examples, but the invention should not be construed as limited to these examples.

Synthesis Example 1: Synthetic Resin (pol-1)

In a nitrogen stream, 61.2 parts by mass of cyclohexanone was charged in a three-necked flask, and heated at 80 °C. Subsequently, a monomer (15.0 parts by mass) corresponding to the unit 1 shown below, a monomer corresponding to the unit 5 shown below (3.54 parts by mass), and a monomer corresponding to the unit 22 shown below (for the following) will be contained for 4 hours ( 12.3 parts by mass) and 1.38 parts by mass of a mixture of 2,2'-azobisisobutyric acid dimethyl ester [V-601, produced by Wako Pure Chemical Industry Co., Ltd.] and cyclohexanone (113.6 parts by mass) The drops were added to the flask. After the dropwise addition was completed, the reaction was allowed to proceed for an additional 2 hours at 80 °C. The reaction solution was allowed to stand to cool, reprecipitated and filtered in a large amount of heptane/ethyl acetate (8/2 by mass), and the obtained solid was dried under vacuum to obtain 27.4 parts by mass of a resin (pol-1). The obtained resin (pol-1) had a weight average molecular weight of 12,000, a polydispersity (Mw/Mn) of 1.6, and a composition ratio measured by ¹³ C-NMR of 45/10/45.

The resin (pol-2) to (pol-35) was synthesized by the same operation as in Synthesis Example 1.

With respect to the resins (pol-1) to (pol-35), the repeating unit (unit), composition ratio (mole ratio), weight average molecular weight (Mw), and polydispersity are shown in Tables 4 to 7 below. The number in the composition ratio corresponds to the left side Repeat unit.

[Preparation of resin composition]

The components shown in the following Table 8 and Table 9 were dissolved in a solvent to prepare a resist solution, and the solution was filtered through a polyethylene filter having a pore size of 0.03 μm to prepare a resin composition (resist composition). . The solid content concentration of each resin composition is appropriately adjusted in the range of 2.0% by mass to 7.0% by mass so that the composition can be applied to the thickness shown in Tables 10 to 12 below.

^* In this table, (% by mass) is the value based on the total solid content of the composition; the same is true hereinafter.

The components and abbreviations in Table 8 and Table 9 are as follows.

[acid generator]

[alkaline compound]

[additive (surfactant)]

W-1: Meg Vanes F176 (produced by Dainippon Ink and Chemicals, Inc.; fluorine)

W-2: Meg Vanes R08 (produced by Dainippon Ink Chemical Co., Ltd.; fluorine-containing and containing antimony)

W-3: Polyoxane polymer KP-341 (produced by Shin-Etsu Chemical Co., Ltd.; containing antimony)

W-4: Troysol S-366 (produced by Troy Chemical Company)

W-5: KH-20 (produced by Asahi Glass Co., Ltd.)

W-6: PolyFox PF-6320 (produced by OMNOVA solution inc.; fluorine)

[solvent]

SL-1: Propylene glycol monomethyl ether acetate (PGMEA)

SL-2: Propylene glycol monomethyl ether propionate

SL-3: ethyl lactate

SL-4: Propylene Glycol Monomethyl Ether (PGME)

SL-5: cyclohexanone

SL-6: γ-butyrolactone

SL-7: propyl carbonate

SL-8: 4-methyl-2-pentanol

SL-9: isobutyl isobutyrate

SL-10: diisoamyl ether

[developer / rinse solution]

D-1: butyl acetate

D-2: Amyl acetate

D-3: 2-heptanone

D-5: 4-methyl-2-pentanol

D-6: decane

D-7: octane

D-8: 1-hexanol

The prepared resin composition was evaluated by the following method.

[KrF exposure example] (Example 1 to Example 30 and Comparative Example 1 and Comparative Example 2)

Applying HMDS (hexamethyldioxane) treatment (110 ° C, 35 seconds) to the surface of the wafer, and coating the first resin composition (resist composition) shown in Table 10 below On the surface, and baked under the conditions shown in Table 10 below (Pre-Bake; PB), a first layer (lower layer) resist film having the thickness shown in Table 10 below was formed. Subsequently, a second resist composition was applied onto the obtained first layer resist film, and baked (prebaked; PB) under the conditions shown in Table 10 below, and formed in the following Table 10. A second (upper) resist film of the thickness shown. In this way, a wafer in which two layers of resist film layers are stacked is obtained.

By using a KrF excimer laser scanner (PAS5500/850, manufactured by ASML) (NA: 0.80), via a line-gap pattern having a light-shielding portion width of 175 nm and an open portion width of 263 nm A binary mask is used to sequentially expose the obtained wafer. Thereafter, the wafer is baked under the conditions shown in Table 10 below (post-exposure baking; PEB) was developed by pudding the organic developer shown in Table 10 for 30 seconds, rinsed by rinsing the rinsing solution shown in Table 10 below, and then rotated at a rotation speed of 4,000 rpm. For 30 seconds, a line-gap (3:2) pattern with a pitch of 438 nm and a gap width of 175 nm (line width: 263 nm) was obtained.

[ArF Exposure Example A] (Example 31 to Example 44 and Comparative Example 3)

An organic anti-reflection film ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was coated on a tantalum wafer and baked at 205 ° C for 60 seconds to form an anti-reflection film having a thickness of 86 nm. And the first resist composition shown in the following Table 11 was coated on the anti-reflection film and baked under the conditions shown in Table 11 below (prebaking: PB) to have the following Table 11 The first layer (lower layer) resist film of the thickness shown. Subsequently, a second resist composition was coated on the obtained first layer resist film and baked (prebaked: PB) under the conditions shown in Table 11 below, and formed as shown in Table 11 below. A second (upper) resist film of the thickness shown. In this way, a wafer in which two layers of resist film layers are stacked is obtained.

By using an ArF excimer laser scanner (PAS5500/1100, manufactured by ASML) (NA: 0.75), via a line-gap pattern having a light-shielding portion width of 175 nm and an open portion width of 263 nm The mask is used to successively expose the obtained wafer. Thereafter, the wafer was baked under the conditions shown in the following Table 11 (post-exposure baking; PEB), developed by overlying the organic developer shown in Table 11 for 30 seconds, by covering the following Table 11 Rinse the rinse solution, then rotate at 4,000 rpm Rotate at a rotation speed for 30 seconds to obtain a line-gap (3:2) pattern (line width: 263 nm) having a pitch of 438 nm and a gap width of 175 nm.

[ArF exposure example B] (Examples 45 to 52 and Comparative Example 4)

An organic anti-reflection film ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was coated on a tantalum wafer and baked at 205 ° C for 60 seconds to form an anti-reflection film having a thickness of 86 nm. And the first resist composition shown in Table 12 below was coated on the anti-reflection film and baked under the conditions shown in Table 12 below (prebaking: PB) to form the following Table 12 The first layer (lower layer) resist film of the thickness shown. Subsequently, a second resist composition was applied onto the obtained first layer of resist film, and baked under the conditions shown in Table 12 below (prebaking: PB) to have the following Table 12 A second (upper) resist film of the thickness shown. In this way, a wafer in which two layers of resist film layers are stacked is obtained.

By using an ArF excimer laser scanner (PAS5500/1100, manufactured by ASML) (NA: 0.75), via a half-line pattern having a light-shielding portion width of 72 nm and an open portion width of 72 nm A halftone mask is used to sequentially expose the obtained wafers. Thereafter, the wafer was baked under the conditions shown in Table 12 below (post-exposure baking; PEB), developed by overlying the organic developer shown in Table 12 for 30 seconds, by covering the following Table 12 The rinsing solution was rinsed, and then rotated at a rotation speed of 4,000 rpm for 30 seconds to obtain a line-gap (3:2) pattern having a pitch of 144 nm and a gap width of 58 nm (line width: 86 奈Meter).

[Contour evaluation method]

The cross-sectional profile of the obtained line-gap (3:2) pattern was evaluated by using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation. Among the 10 pattern profiles observed, the size of the top (outermost surface) of the pattern and the size of the bottom (the interface with the substrate) were measured, and the ratio of the top size to the bottom size was taken as the contour index. In the calculated contour index, a value close to 1 indicates a rectangular contour, a value greater than 1 indicates an overcut contour, and a value less than 1 indicates a wedge contour. In fact, when the value is from 0.9 to 1.1, the outline can be declared to be rectangular.

[LWR evaluation method]

The obtained line-gap (3:2) pattern was observed using a critical dimension scanning electron microscope (SEM: S-9380II, manufactured by Hitachi Ltd.), and has a rule in the range of 2 μm in the longitudinal direction of the gap pattern. The line width is measured at 50 points of the interval. The 3σ is calculated based on its standard deviation, thereby measuring the roughness. The smaller the value, the higher the performance.

The results of the KrF exposure example and the results of ArF exposure example A and ArF exposure example B are shown in Table 10, Table 11, and Table 12, respectively.

As is apparent from Table 10 showing the results of the KrF exposure example, in Comparative Example 1 and Comparative Example 2 in which a pattern was formed by forming a single-layer resist film, the outline was an overcut profile and the LWR was large.

On the other hand, in Examples 1 to 30 in which a pattern was formed by stacking two resist film layers, it was found that the outline was rectangular and at the same time, the LWR was small.

As is apparent from Table 11 showing the results of ArF exposure example A, in Comparative Example 3 in which a pattern was formed by forming a single-layer resist film, the outline was an overcut profile and the LWR was large.

On the other hand, in Examples 31 to 44 in which a pattern was formed by stacking two resist film layers, it was found that the outline was rectangular and at the same time, the LWR was small.

As is apparent from Table 12 showing the results of ArF exposure example B, in Comparative Example 4 in which a pattern was formed by forming a single-layer resist film, the outline was an overcut profile and the LWR was large.

On the other hand, in Examples 45 to 59 in which a pattern was formed by stacking two resist film layers, it was found that the outline was a rectangle, and at the same time, the LWR was small.

In summary, in Example 45, Example 46, Example 56 to Example 58, where SP1 - SP2 satisfies Equation (3) and BR1/BR2 satisfies Equation (4), and Equation (1) and BR1/1 are satisfied in SP1 - SP2 In Example 47, Example 48, and Example 53 to Example 55 in which BR2 satisfies the formula (2), the squareness of the outline is particularly excellent, and at the same time, the LWR is also particularly small.

Industrial applicability

According to the present invention, it is possible to provide a pattern forming method capable of forming a pattern having a good LWR while having a rectangular outline, a multilayer resist pattern formed by the method, a multilayer film for organic solvent development suitable for the pattern forming method, A resist composition, a method of manufacturing an electronic component, and an electronic component which are suitable for the pattern forming method.

The present application is based on a Japanese patent application filed on June 30, 2011 (Japanese Patent Application No. 2011-146861), and a US patent provisional application filed on June 30, 2011 (U.S. Patent Provisional Application No. 61) Japanese Patent Application No. 2012-143050, filed on Jun. 26, 2012, the content of which is hereby incorporated by reference.

Claims (12)

A pattern forming method comprising: (i) a step of forming a first film on a substrate by using a first resin composition (I); (ii) by using a second resin composition (II) at the first a step of forming a second film on the film, the second resin composition (II) being different from the resin composition (I); (iii) exposing the multilayer film having the first film and the second film And (iv) developing the exposed first film and the second film in the multilayer film by using an organic solvent-containing developer to form a negative pattern. The pattern forming method according to claim 1, wherein the resin contained in the first resin composition (I) is different from the resin contained in the second resin composition (II). The pattern forming method according to claim 1, wherein the resin contained in at least one of the first resin composition (I) and the second resin composition (II) has a function of being capable of being acid Decomposes a repeating unit that produces a group of polar groups. The pattern forming method according to any one of claims 1 to 3, wherein a solubility parameter SP1 of the resin contained in the first resin composition (I) and the second resin The solubility parameter SP2 of the resin contained in the composition (II) has a relationship of the following formula (1), and the resin contained in the first resin composition (I) has a ability to decompose under the action of an acid The repeating unit of the group which generates a polar group has a molar ratio of BR1 in terms of all repeating units in the resin, and the resin contained in the second resin composition (II) has an ability to be in acid The repeating unit which decomposes to generate a group of a polar group has a molar ratio of BR2 in terms of all repeating units in the resin, and BR1 has a relationship of the following formula (2) with BR2: ):-0.6(MPa) ^1/2 <SP1-SP2 1 (MPa) ^1/2 ; Formula (2): BR1/BR2>1. The pattern forming method according to any one of claims 1 to 3, wherein a solubility parameter SP1 of the resin contained in the first resin composition (I) and the second resin The solubility parameter SP2 of the resin contained in the composition (II) has a relationship of the following formula (3), and the resin contained in the first resin composition (I) has a ability to decompose under the action of an acid The repeating unit of the group generating the polar group has a molar ratio of BR1 based on all the repeating units in the resin, and the resin contained in the second resin composition (II) has the ability to act under the action of an acid The repeating unit which decomposes the group which generates a polar group has a molar ratio of BR2 based on all the repeating units in the resin, and has a relationship of the following formula (4) between BR1 and BR2: Formula (3): SP1- SP2>1 (MPa) ^1/2 ; Formula (4): BR1/BR2>0.2. The pattern forming method according to any one of claims 1 to 3, wherein the first resin composition (I) and the second tree At least one of the lipid compositions (II) contains a compound capable of generating an acid upon irradiation with actinic rays or radiation. The pattern forming method according to claim 6, wherein the second resin composition (II) contains a compound capable of generating an acid upon irradiation with actinic rays or radiation. The pattern forming method according to any one of claims 1 to 3, wherein the organic solvent-containing developer contains at least one of a ketone solvent, an ester solvent, an alcohol solvent, and a guanamine. A developer of an organic solvent selected from the group consisting of a solvent and an ether solvent. A multilayer resist pattern formed by the pattern forming method according to any one of claims 1 to 3. A multilayer film for organic solvent development comprising: a first film formed on a substrate by using the first resin composition (I); and a second resin composition different from the resin composition (I) (II) a second film formed on the first film. A method of producing an electronic component, comprising the pattern forming method according to any one of claims 1 to 3. An electronic component manufactured by the method of manufacturing an electronic component according to claim 11 of the patent application.